JP2022553090A - Crystallizable Shrinkable Films and Thermoformable Films and Sheets Made from Reactor Grade Resins with Recycles - Google Patents

Abstract

The present disclosure provides terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in specific composition ranges with specific advantages and improved properties. Crystallizable shrinkable films and thermoformable films or sheets comprising amorphous polyester compositions containing residues of The present disclosure further provides recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled Crystallizable shrinkable films and thermoformable films and/or sheets comprising residues of recycled ethylene glycol (EG) and recycled diethylene glycol (DEG). [Selection figure] None

Description

Field of Invention

[0001] The present disclosure provides terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and ethylene glycol (EG) within specific compositional ranges with particular advantages and improved properties. Crystallizable shrinkable films and thermoformable films and/or sheets comprising polyester compositions containing residues of diethylene glycol (DEG). The present disclosure further provides recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled Crystallizable shrinkable films and thermoformable films and/or sheets comprising polyester compositions comprising residues of recycled ethylene glycol (EG) and recycled diethylene glycol (DEG).

[0002] The following desirable shrink film properties are: (1) a low shrink onset temperature; (2) a shrink rate that increases gradually and in a controlled manner with increasing temperature over the temperature range where 3) low enough shrink force to prevent collapse of the underlying container; (4) high maximum shrinkage (shrinkage at highest temperature), e.g. (5) low shrinkage in the direction perpendicular to the direction of high shrinkage; (6) high toughness of the film to prevent unwanted crushing, breaking, tearing, splitting, foaming, or wrinkling of the film during manufacture and before and after shrinkage; (7) recyclability; and (8) recyclability.

[0003] There is a commercial need for thermoformable films or sheets that have excellent film or sheet properties and recyclability and/or recyclables.

gist of the invention

[0004] The specific combination of glycol monomers in the shrink film resin composition can produce films with excellent shrink film performance, and further crystallize so as not to affect the recycling of PET flakes during recycling. turned out to be possible. These crystallizable shrink film resins can be processed with PET bottles and become a component of recyclable PET flakes after the recycling process is completed. It has been found that the selection of a particular combination of glycol monomers and their amounts are important for producing films with excellent shrink film properties and for producing crystallizable films. The optimized polyester resin compositions of the present disclosure are amorphous but crystallizable. Thus, while these compositions exhibit excellent properties in film applications, including shrink films, these strain-induced crystals have high melting points, providing compatibility with recycling processes. The shrink film label of the present disclosure does not need to be removed during the recycling process and does not affect the recycling process.

[0005] Heat-shrinkable films must meet various compliance criteria for use in order to perform in this application. The film should be tough, shrink in a controlled manner, and provide sufficient shrink force to hold itself to the bottle surface without crushing the contents. Additionally, when these labels are applied to polyester containers, the polyester shrink film labels must not interfere with the bottle recycling process. The shrink film of the present disclosure is advantageous because the label can be recycled along with the bottle or container. Therefore, the entire bottle, including the label, can be recycled and converted into new products without additional operational requirements or new environmental concerns. Heat shrinkable films are made from a variety of raw materials to meet a range of material demands. This disclosure describes the unique and unexpected effects addressed by certain monomer combinations on shrink film resin compositions.

[0006] Polyester shrink film compositions have been used commercially as shrink film labels for food, beverages, personal items, household items, and the like. Often these shrink films are used in combination with transparent polyethylene terephthalate (PET) bottles or containers. After use, the entire product (bottle and label) goes into the recycling process. At a typical recycling site, PET and shrink film materials are often mixed at the end of the process due to their similar composition and density. Drying of the PET flakes is necessary to remove residual water adhering to the PET during the recycling process. Typically PET is dried at temperatures in excess of 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, and the PET flakes often form agglomerates. These agglomerates must be removed prior to further processing. These agglomerates reduce the yield of PET flakes from this process and require additional handling steps.

[0007] In addition, combinations of certain glycol monomers in film or sheet resin compositions can produce films or sheets with superior performance characteristics, and these combinations also allow films or sheets to be recycled from PET flakes. It was found to be crystallizable without affecting the These crystallizable film or sheet resins can be processed with recycled PET and ultimately become a component of recyclable PET flakes after the recycling process is completed. The selection of specific combinations of glycol monomers and their amounts have been found to be important for producing films or sheets with superior performance characteristics and for producing crystallizable films or sheets. The optimized polyester resin compositions of the present disclosure are amorphous, but crystallizable. As such, these compositions exhibit excellent properties in film or sheet applications such as formed, thermoformed, or as-molded parts and/or articles, where they have high strain-induced crystalline melting points and are Can be recycled. The films or sheets of the present disclosure do not need to be removed during the recycling process and do not affect the recycling process.

[0008] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the ( a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mole % terephthalic acid residues and (ii) from about 0 to about 30 mole % aromatic and/or aliphatic having up to 20 carbon atoms Comprising dicarboxylic acid residues, the (b) diol component comprises at least about 75 mol % ethylene glycol residues and (i) from about 0 to less than about 24 mol % neopentyl glycol residues, (ii) about 0 about 25 mole percent of 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mole percent of total diethylene glycol residues in the final polyester composition. mol% or less of other glycols, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, or the (b) diol component is about 75 mol % or more ethylene glycol residues, and (i) from about 0.1 to less than about 24 mol % neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol % 1,4-cyclohexane di methanol residues, and (iii) from about 1 to less than about 10 mole percent of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition, up to about 25 mole percent, wherein dicarboxylic The total mol % of the acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0009] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the ( a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mole % terephthalic acid residues and (ii) from about 0 to about 30 mole % aromatic and/or aliphatic having up to 20 carbon atoms Comprising dicarboxylic acid residues, the (b) diol component comprises at least about 75 mol % ethylene glycol residues and (i) less than about 15 mol % neopentyl glycol residues, (ii) less than about 5 mol % and (iii) up to about 25 mole percent of other glycols, including less than about 5 mole percent of one or more of the total diethylene glycol residues in the final polyester composition. , where the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent.

[0010] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the ( a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mole % terephthalic acid residues and (ii) from about 0 to about 30 mole % aromatic and/or aliphatic having up to 20 carbon atoms Comprising dicarboxylic acid residues, the (b) diol component comprises at least about 80 mole % ethylene glycol residues and (i) from about 5 to less than about 17 mole % neopentyl glycol residues, (ii) about 2 about 20 moles containing one of from to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole percent of total diethylene glycol residues in the final polyester composition % of other glycols, where the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0011] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the ( a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mole % terephthalic acid residues and (ii) from about 0 to about 30 mole % aromatic and/or aliphatic having up to 20 carbon atoms Comprising dicarboxylic acid residues, the (b) diol component comprises about 76 mol % or more of ethylene glycol residues and (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) a final about 24 mol % or less of an amorphous component comprising one or more of the total diethylene glycol residues in the polyester composition, wherein the total mol % of the dicarboxylic acid component is 100 mol %, and the total mol % of the diol component is Mole % is 100 mol %.

[0012] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the ( a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mole % terephthalic acid residues and (ii) from about 0 to about 30 mole % aromatic and/or aliphatic having up to 20 carbon atoms Comprising dicarboxylic acid residues, the (b) diol component comprises at least about 75 mol % ethylene glycol residues and (i) from about 10 to less than about 15 mol % neopentyl glycol residues, (ii) about 1 about 25 containing one or more of from to less than about 5 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole percent total diethylene glycol residues in the final polyester composition. mol% or less of other glycols, where the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0013] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. groups, the (b) diol component, whether formed in situ or not, (i) from about 0 to about 30 mol % of neopentyl glycol residues, (ii) from about 0 to about 30 mol % 1,4-cyclohexanedimethanol residues, and (iii) diethylene glycol residues, and the balance of the glycol component is (iv) ethylene glycol residues and (v) optionally 0 to 10 mol % or 0-5 mol % of at least one modified glycol residue, wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0014] An embodiment of the present disclosure is a crystallizable film of any of the preceding embodiments, wherein the film is stretched in at least one direction, and the stretched film is strained at 190°C or more or 200°C or more. It has an induced crystalline melting point.

[0015] One embodiment of the present disclosure is an extruded or calendered film comprising the crystallizable film of any of the preceding embodiments.
[0016] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. wherein the (b) diol component comprises from about 75 mol % or more ethylene glycol residues and (i) from about 0 to less than about 24 mol % neopentyl glycol residues, (ii) from about 0 to about 24 up to about 25 mol % containing one or more of less than 1,4-cyclohexanedimethanol residues and (iii) from about 1 to less than about 10 mol % of total diethylene glycol residues in the final polyester composition. wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %, or the (b) diol component is about 75 mol % or more and (i) from about 0.1 to less than about 24 mol % neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol % 1,4-cyclohexanedimethanol residues. and (iii) from about 1 to less than about 10 mole percent of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition, and up to about 25 mole percent of the dicarboxylic acid component. The total mol % is 100 mol % and the total mol % of the diol component is 100 mol %.

[0017] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. wherein the (b) diol component comprises about 75 mol % or more of ethylene glycol residues and (i) about 15 mol % or less of neopentyl glycol residues; (ii) about 5 mol % or less of 1, 4-cyclohexanedimethanol residues, and (iii) up to about 25 mole percent of other glycols, including up to about 5 mole percent of one or more of the total diethylene glycol residues in the final polyester composition, wherein The total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0018] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. groups wherein the (b) diol component comprises at least about 80 mol % ethylene glycol residues and (i) from about 5 to less than about 17 mol % neopentyl glycol residues, (ii) from about 2 to about 10 up to about 20 mol % containing one or more of the following: less than 1 mol % of 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 5 mol % of total diethylene glycol residues in the final polyester composition. wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0019] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. groups wherein the (b) diol component contains about 76 mole percent or more of ethylene glycol residues, and (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) the final polyester composition. up to about 24 mol % amorphous component comprising one or more diethylene glycol residues in the dicarboxylic acid component is 100 mol % total diol component is 100 mol % in mol %.

[0020] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. groups wherein the (b) diol component comprises at least about 75 mole percent ethylene glycol residues and (i) from about 10 to less than about 15 mole percent neopentyl glycol residues, (ii) from about 1 to about 5 up to about 25 mol % containing one or more of less than 1 mol % of 1,4-cyclohexanedimethanol residues and (iii) from about 1 to less than about 5 mol % of total diethylene glycol residues in the final polyester composition wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0021] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic The acid component comprises (i) about 70 to about 100 mole percent terephthalic acid residues and (ii) about 0 to about 30 mole percent aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. groups, the (b) diol component, whether formed in situ or not, (i) from about 0 to about 30 mol % of neopentyl glycol residues, (ii) from about 0 to about 30 mol % 1,4-cyclohexanedimethanol residues, and (iii) diethylene glycol residues, and the balance of the glycol component is (iv) ethylene glycol residues and (v) optionally 0 to 10 mol % or 0-5 mol % of at least one modified glycol residue, wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %.

[0022] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising the film or sheet of any of the preceding embodiments.
[0023] One embodiment of the present disclosure includes medical devices, medical packaging, health care products, commercial food service products, trays, containers, food plates, tumblers comprising the film or sheet of any of the preceding embodiments. , storage boxes, bottles, cookware, blenders and mixing bowls, household items, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys.

[0024] One embodiment of the present disclosure is an article of manufacture comprising a thermoformed film or sheet according to any of the preceding claims.
[0025] One embodiment of the present disclosure is a method of making a thermoformed film or sheet of any of the preceding embodiments, the method comprising the steps of: A) heating the polyester film or sheet; Applying pneumatic, vacuum, and/or physical pressure to the softened film or sheet, C) conforming the sheet to the shape of the mold by vacuum or pressure, and D) removing the thermoformed part or article from the mold. Including process.

[0026] One aspect of this disclosure is the process of preparing the polyesters of the present invention from recycled polyesters. One aspect of the present disclosure is a process for preparing a copolyester from a recycled polyester and/or a recycled copolyester.

[0027] In one aspect, the present disclosure provides (A) a recycled and/or recycled polyester whose acid component consists of at least 70 mol% terephthalic acid and whose diol component consists of at least 70 mol% ethylene glycol. or (B) the acid component of which consists of at least 70 mol % of terephthalic acid, and at least 70 mol % of the diol component of which has a molar ratio of 96:3:1 to 20:68:12. a recycled copolyester consisting of a mixture of ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol; 70 mol % of ethylene glycol (EG), diethylene glycol (DEG), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG) or 2,2,4,4-tetramethyl-1,3-cyclobutane A recycled copolyester consisting of a mixture of two or more glycols, including a diol (TMCD), butanediol, and isosorbide, or (D) the acid component of which consists of at least 70 mol % terephthalic acid, and the diol. At least 70 mole percent of the components are linear from any recycled copolyester consisting of a mixture of ethylene glycol and 1,4-cyclohexanedimethanol in a molar ratio of 3.5:96.5 to 100:0. A process for preparing a high molecular weight copolyester is provided.

[0028] This process provides high polymerization rates and the polymers so produced are used in the production of plastics, fibers, films, shrinkable films, sheets, molded articles and other molded articles with excellent physical properties. can be used for In one aspect, the disclosed process converts factory and consumer waste products into high quality copolyester resins that can be used to make novel plastics with high levels of recycled content. explains how. In another aspect, the disclosed process describes a method of converting factory and consumer waste products into resins that can be used to make high quality shrinkable films.

[0029] One aspect of the present disclosure is a process for making a copolyester from a recycled copolyester, the process comprising:
(a) recycled PET, recycled PETG, recycled PCT, recycled PCTG, recycled PCTA, recycled PCTM, and/or recycled PETM, terephthalic acid (TPA), and ethylene glycol introducing (EG) into a paste bath, stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) in the first reaction zone; and optionally additional recycled PET, recycled PETG, recycled PCTM, and/or recycled PETM, and terephthalic acid (TPA) and ethylene adding glycol (EG) in an EG:TPA molar ratio of 1:1 to 4:1 and optionally adding a catalyst;
(d) reacting TPA with EG and at least one additional glycol (such as CHDM) in a first reaction zone at a melt temperature of at least 200° C. and a pressure of up to 40 psi to form oligomers and unreacted producing a first esterification product comprising TPA, EG, and an additional glycol (such as CHDM);
(e) delivering the first esterification product to a second reaction zone;
(f) esterification of unreacted TPA, EG, and additional glycol (such as CHDM) in the first esterification product in a second reaction zone at a melt temperature of at least 200° C. and a pressure of up to 20 psi; to produce a second esterification product comprising a copolyester oligomer;
(g) delivering the second esterification product to a third reaction zone;
(h) polycondensing the second esterification product in a third reaction zone, optionally in the presence of a polycondensation catalyst, to produce a prepolymerized product comprising a copolyester; and (i) delivering the prepolymerized product to one or more finishing zones;

[0030] One aspect of the present disclosure is a process for making a copolyester from a recycled copolyester, the process comprising:
(a) introducing recycled PET, recycled PETG, recycled PCT, recycled PCTG, or recycled PCTA, as well as terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), DEG, or neopentyl glycol (NPG), and optionally adding of recycled PET, recycled PETG, recycled PCT, recycled PCTG, or recycled PCTA, and terephthalic acid (TPA) and ethylene glycol (EG) at a molar ratio of EG:TPA of 1:1. ~4:1 optionally in the presence of an esterification catalyst;
(d) reacting TPA with EG and at least one additional glycol (such as CHDM) in a first reaction zone at a melting temperature of at least 200° C. and a pressure of up to 40 psi to form oligomers and unreacted TPA; , EG, and an additional glycol (such as CHDM and/or NPG and/or DEG);
(e) delivering the first esterification product to a second reaction zone;
(f) esterification of unreacted TPA, EG, and additional glycol (such as CHDM) in the first esterification product in a second reaction zone at a melt temperature of at least 200° C. and a pressure of up to 20 psi; to produce a second esterification product comprising a copolyester oligomer;
(g) delivering the second esterification product to a third reaction zone;
(h) polycondensing the second esterification product in a third reaction zone, optionally in the presence of a polycondensation catalyst, to produce a prepolymerized product comprising a copolyester; and (i) delivering the prepolymerized product to one or more finishing zones;

[0031] One aspect of the disclosure is the process of any one of the preceding aspects, the process further comprising adding a catalyst or additive with the addition of the recycled polyester, wherein the catalyst or additive Agents are components in recycled polyesters such as Sb, Ti, Co, Mn, Li, Al, and P.

[0032] One aspect of the present disclosure is a method of introducing or forming recycled content in a polyester produced by the process of the preceding aspect, the method comprising:
(a) obtaining a recycled monomer quota or limit for at least one recycled monomer comprising TPA, EG, DMT, CHDM, NPG, or DEG;
(b) converting the recycled monomers during the synthesis process to produce a polyester;
(c) designating at least a portion of the polyester as corresponding to at least a portion of a recycled monomer quota or limit; marketing or selling the polyester as containing or obtained using a content thereof.

[0033] FIG. 1 is a differential scanning calorimeter thermogram showing the melting point of the first thermal strain-induced crystal of Embrace LV. [0034] Figure 2 shows the shrinkage properties of films produced using Embrace LV (10 second dwell time). [0035] Figure 3 shows shrink performance. [0036] Figure 4 is a DSC thermogram of Film N stretched at a first heat of 80°C. [0037] Figure 5 is a DSC thermogram of Film N stretched at a second heat of 80°C. [0038] Figure 6 is a flow diagram of various processes according to the present disclosure. [0039] Figure 7 shows the concentration of Sb catalyst in the final material as a function of the loading concentration of the rPET (recycled PET) starting material.

[0040] The present disclosure may be understood more readily by reference to the following detailed description of specific embodiments and examples of the present disclosure. For purposes of the present disclosure, specific embodiments of the present disclosure are set forth in the Summary of the Invention and further described herein as follows. Other implementations of the disclosure are also described herein.

[0041] Heat-shrinkable plastic films are used as coverings to hold objects together and as outer packaging for bottles, cans, and other types of containers. For example, the film is used to cover the lid, neck, shoulder, body, or the entire bottle for labeling, protecting, packaging, or enhancing the value of the product, and for other reasons. In addition, the film can be used as a covering for packaging objects such as boxes, bottles, boards, sticks, or notebooks together as a group, and the film can also be adhered tightly as wrapping. The uses described above take advantage of the film's shrinkability and internal shrinkage stress.

[0042] Historically, polyvinyl chloride (PVC) films have dominated the shrink film market. However, polyester film has become a viable alternative because it does not have the environmental concerns associated with PVC film. Polyester shrink film ideally has properties very similar to PVC film, so polyester film can serve as a "drop-in" replacement film and can be processed in existing heat shrink tunnel equipment. . Desirable PVC film properties for replicas include (1) a relatively low shrink onset temperature, (2) a total shrinkage that increases gradually and in a controlled manner with increasing temperature, and (3) underlying (4) high total shrinkage (e.g., 50% or greater); (5) inherent film toughness to prevent useless tearing and splitting of the film before and after shrinkage; and (6) a high strain-induced crystal melting point;

[0043] Heat-shrinkable films must satisfy various compliance criteria for use in order to be viable in this application. The film should be tough, shrink in a controlled manner, and provide sufficient shrink force to hold itself to the bottle surface without crushing the contents. Furthermore, when these labels are attached to polyester containers, these labels must not interfere with the recycling process of PET bottles. Indeed, the label is also recyclable, provided that the entire bottle can be recycled and transformed into new products without additional operational requirements or new environmental concerns. would be convenient. Heat shrinkable films are manufactured from a variety of raw materials to meet a range of material demands. This disclosure describes the unique and unexpected effect addressed by the combination of certain monomers that improve the recyclability of labels made from polyester shrink films.

[0044] Shrink film compositions are used commercially as shrink film labels for food, beverages, personal items, household items, and the like. Often these shrink films are used in combination with clear polyethylene terephthalate (PET) bottles or containers. The entire product (bottle and label) is then put into the recycling process. At a typical recycling site, PET and shrink film materials are often mixed at the end of the process due to their similar composition and density. Drying the PET flakes is necessary to remove residual water adhering to the PET during the recycling process. Typically PET is dried at temperatures in excess of 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming agglomerates with the PET flakes. These agglomerates must be removed prior to further processing. These agglomerates reduce the yield of PET flakes from this process and require additional handling steps.

[0045] The specific combination of glycol monomers in the shrink film resin composition allows the production of films with superior shrink film properties, yet does not affect the recycling of PET flakes during the recycling process. It was found that it can be crystallized at These crystallizable shrink film resins can be processed with PET bottles and become a component of recyclable PET flakes after the recycling process is completed. The selection of specific combinations of glycol monomers and their amounts have been found to be important in producing films with excellent shrink film properties and crystallizable films.

[0046] As used herein, the term "polyester" is intended to include "copolyesters", in which one or more difunctional carboxylic acids and/or multifunctional carboxylic acids are is intended to mean a synthetic polymer prepared by reaction with a difunctional hydroxyl compound and/or a polyfunctional hydroxyl compound, such as a branching agent. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a dihydric alcohol such as glycols and diols. The term "glycol" as used herein includes, but is not limited to, diols, glycols, and/or polyfunctional hydroxyl compounds such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound has an aromatic nucleus bearing two hydroxyl substituents, such as hydroquinone. may As used herein, the term "residue" means any organic structure incorporated into a polymer by polycondensation and/or esterification reactions from the corresponding monomer. As used herein, the term "repeat unit" means an organic structure having a dicarboxylic acid residue and a diol residue linked through an ester group. Thus, for example, dicarboxylic acid residues may be derived from dicarboxylic acid monomers or their associated acid halides, esters, salts, anhydrides, and/or mixtures thereof. Additionally, the term "diacid" as used herein includes polyfunctional acids such as branching agents. Thus, the term "dicarboxylic acid" as used herein includes dicarboxylic acids useful for reaction processing with diols to give polyesters, as well as related acid halides, esters, half-esters, salts, half-salts, anhydrides. are intended to include any dicarboxylic acid derivatives such as dicarboxylic acids, mixed anhydrides, and/or mixtures thereof. As used herein, the term "terephthalic acid" refers to terephthalic acid itself and its residues, as well as related acid halides, esters, half-esters, salts, half- It is intended to include any terephthalic acid derivative such as salts, anhydrides, mixed anhydrides, and/or mixtures thereof or residues thereof.

[0047] Polyesters used in this disclosure can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of the present disclosure contain a substantially equimolar ratio of acid residues (100 mole %) and diol (and/or multifunctional hydroxyl compound) residues such that the total moles of repeat units equals 100 mole %. It may contain groups (100 mol %). Thus, the mole percentages given in this disclosure may be based on total moles of acid residues, total moles of diol residues, or total moles of repeat units. For example, a polyester containing 10 mol % isophthalic acid based on total acid residues means that the polyester contains 10 mol % isophthalic acid residues out of 100 mol % total acid residues. That is, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 25 mol% 1,4-cyclohexanedimethanol based on total diol residues is 1,4-cyclohexanedimethanol in which the polyester contains 25 mol% 1,4-cyclohexanedimethanol out of 100 mol% total diol residues. It is meant to contain methanol residues. That is, there are 25 moles of 1,4-cyclohexanedimethanol residues for every 100 moles of diol residues.

[0048] In certain embodiments, terephthalic acid or esters thereof, such as dimethyl terephthalate or mixtures of terephthalic acid residues and esters thereof, are added to the dicarboxylic acid component used to form the polyesters useful in this disclosure. You may constitute a part or the whole. In certain embodiments, terephthalic acid residues may constitute part or all of the dicarboxylic acid component used to form the polyesters useful in this disclosure. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in this disclosure. or 80 to 100 mol%; or 90 to 100 mol%; or 99 to 100 mol%; or 100 mol% of terephthalic acid and/or dimethyl terephthalate and/or Mixtures thereof may also be used.

[0049] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in this disclosure may be up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more of modified aromatic dicarboxylic acids. Yet another embodiment contains 0 mole % modified aromatic dicarboxylic acid. Thus, when present, the amount of one or more modified aromatic dicarboxylic acids may be within any range of these above mentioned end point values, eg, 0.01 to 10 mole %, 0.01 to 5 mole %, 0.01 to 10 mole %, 0.01 to 5 mole %, 0.01 to 10 mole %, 0.01 to 5 mole %, It is believed that it may vary from 01 to 1 mole percent. In one embodiment, modified aromatic dicarboxylic acids that may be used in the present disclosure include, but are not limited to, those that have up to 20 carbon atoms and can be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2, 7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and their esters. In one embodiment the modified aromatic dicarboxylic acid is isophthalic acid.

[0050] The carboxylic acid component of the polyesters useful in this disclosure further includes up to 10 mol%, such as up to 5 mol% or up to 1 mol% of one or more aliphatic dicarboxylic acids containing from 2 to 16 carbon atoms. , for example cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and/or dodecanedioic acid. Certain embodiments may also include 0.01 to 10 mol %, such as 0.1 to 10 mol %, 1 or 10 mol %, such as 5 to 10 mol %, of one or more modified aliphatic dicarboxylic acids. . Yet another embodiment contains 0 mole % modified aliphatic dicarboxylic acids. The total mole percent of the dicarboxylic acid component is 100 mole percent. In one embodiment, adipic acid and/or glutaric acid are useful in the present disclosure provided in the modified aliphatic dicarboxylic acid component of the polyester.

[0051] Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and/or salts may be used in place of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0052] In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in the present disclosure may comprise 1,4-cyclohexanedimethanol. In another embodiment, the diol component of polyester compositions and polyester blend compositions useful in the present disclosure comprises 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis/trans 1,4-cyclohexanedimethanol may vary within the range of 50/50 to 0/100, eg 40/60 to 20/80.

[0053] The diol component of polyester compositions and polyester blend compositions useful in this disclosure includes, but is not limited to, the sum of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition. is 0 to 30 mol%, 1 to 30 mol%, or 1 to 25 mol%, or 1 to 20 mol%, or 1 to 15 mol%, or 1 to 10 mol%, or 2 to 30 mol%, or 2 to 25 mol %, or 2 to 20 mol %, or 2 to 15 mol %, or 2 to 10 mol %, or 3 to 30 mol %, or 3 to 25 mol %, or 3 to 20 mol %, or 3 ~15 mol%, or 3-10 mol%, 4-30 mol%, or 4-25 mol%, 4-20 mol%, or 4-15 mol%, or 4-10 mol%, 5-30 mol% or 6 to 15 mol%, or 6 to 10 mol%, or 7 to 30 mol%, or 7 to 25 mol%, 7 to 20 mol%, or 7 to 15 mol%, or 7 to 10 mol%, or 8 to 30 mol %, or 8 to 25 mol %, or 8 to 20 mol %, or 8 to 15 mol %, or 8 to 10 mol %, or 9 to 30 mol %, or 9 to 25 mol %, or 9 to 20 mol %, or 9-15 mol %, or 9-10 mol %, or 10-30 mol %, or 10-25 mol %, or 10-20 mol %, or 10-15 mol %, or 11-30 mol %, or 11 to 30 mol %, or 11 to 25 mol %, or 11 to 20 mol %, or 11 to 15 mol %, or 12 to 30 mol %, or 12 to 25 mol %, or 12 to 20 mol % , or 12-15 mol %, or 13-30 mol %, or 13-25 mol %, or 13-20 mol %, or 13-15 mol %, or 14-30 mol %, or 14-25 mol %, or 14-20 mol %, or 14-15 mol %, or 15-30 mol %, or 15-25 mol %, or 15-20 mol %, or 16-20 mol %, or 18-20 mol %, or 10-18 mol %, or 16-18 mol %, or 12-16 mol %, or 16-20 mol %, or 14-18 mol %, or 11-30 mol %, or 13-30 mol %, or 14 ~30 mol %, or 10 to 29 mol %, or 11 to 29 mol %, or 12 to 29 mol %, or 13 to 29 mol %, or 14 to 29 mol %, or 15 to 29 mol %, or 10 to 28 mol % , or 11 to 28 mol %, or 12 to 28 mol %, or 13 to 28 mol %, or 14 to 28 mol %, or 15 to 28 mol %. In one embodiment, the sum of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition is from 4 to 15 mol%, or from 2 to 21 mol%, or from 2 to less than 20 mol%. , or 4-20 mol %, or 5-18 mol %, or 10-21 mol %, or 12-21 mol %, where the total mol % of the diol component is 100 mol %.

[0054] In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in this disclosure comprises 0 to 30 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. may contain. In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in the present disclosure may comprise 0 to 25 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. . In one embodiment, the diol component of polyester compositions useful in the present disclosure may comprise 0 to 17 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in the present disclosure may comprise 5 to 20 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. . In one embodiment, the diol component of polyester compositions and polyester blend compositions useful in the present disclosure may comprise 10 to 20 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. . In one embodiment, the diol component of polyester compositions and polyester blend compositions useful in the present disclosure may comprise 10 to 15 mole percent neopentyl glycol, based on the total mole percent of the diol component being 100 mole percent. . In one embodiment, the diol component of polyester compositions and polyester blend compositions useful in the present disclosure may comprise 15 to 25 mol% neopentyl glycol, based on the total mol% of the diol component being 100 mol%. .

[0055] In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in this disclosure is 0 to 30 mol%, 0.01 to 30 mol %, or 0 to 20 mol %, or 0.1 to 20 mol %, or 2 to 20 mol %, or 0.01 to 15 mol %, or 0.01 to 14 mol %, or 0.01 to 13 mol %, or 0.01 to 12 mol %, or 0.01 to 11 mol %, or 0.01 to 10 mol %, or 0.01 to 9 mol %, or 0.01 to 8 mol %, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 3 to 15 mol%, or 3 to 14 mol%, or 3 to 13 mol%, or 3 to 12 mol %, or 3-11 mol %, or 3-10 mol %, or 3-9 mol %, or 3-8 mol %, or 3-7 mol %, or 2-10 mol %, or 2-9 mol %, or 2-8 mol %, or 2-7 mol %, or 2-5 mol %, or 1-7 mol %, or 1-5 mol %, or 1-3 mol % of 1,4-cyclohexane It may contain dimethanol residues.

[0056] In one embodiment, the diol component of the polyester compositions useful in this disclosure is 0.01 to 15 mole percent 1,4-cyclohexanedimethanol, based on the total mole percent of the diol component being 100 mole percent. may include In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0 or more and less than 15 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component being 100 mol%. . In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0.01 to 10 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component being 100 mol%. good. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0 or more and less than 10 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component being 100 mol%. . In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0.01 to 5 mole percent 1,4-cyclohexanedimethanol, based on the total mole percent of the diol component being 100 mole percent. good. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0 or more and less than 5 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component being 100 mol%. .

[0057] Some other diol residues may of course be generated in situ during processing. The total amount of diethylene glycol residues, whether generated in situ during processing or intentionally added, or both, may be present in any amount, such as 100 mol %. 1 to 15 mol %, or 2 to 12 mol %, or 2 to 11 mol %, or 2 to 10 mol %, or 2 to 9 mol %, or 3 to 12 mol %, based on the total mol % of the diol component; or 3 to 11 mol %, or 3 to 10 mol %, or 3 to 9 mol %, or 4 to 12 mol %, or 4 to 11 mol %, or 4 to 10 mol %, or 4 to 9 mol %, or , 5-12 mol %, or 5-11 mol %, or 5-10 mol %, or 5-9 mol % diethylene glycol residues may be present.

[0058] In one embodiment, the total amount of diethylene glycol residues that may be present in the polyesters useful in the present disclosure is either generated in situ during processing, intentionally added, or both. 4 mol % or less; or 3.5 mol % or less; or 3.0 mol % or less; or 2.5 mol % or less; or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol%, or 2 to 8 mol% , or 2 to 7 mol %, or 2 to 6 mol %, or 2 to 5 mol %, or 3 to 8 mol %, or 3 to 7 mol %, or 3 to 6 mol %, or 3 to 5 mol % There may be, or in some embodiments, no intentionally added diethylene glycol residues. In certain embodiments, no modified diol is added to the polyester composition.

[0059] In all embodiments, the balance of the diol component may comprise ethylene glycol residues in any amount, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the polyester portion of the polyester compositions useful in the present disclosure is 50 mol% or more, or 55 mol% or more, or 60 mol% or more, or 65 mol% or more, or 70 mol% or more, or 75 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 95 mol% or more, or 50 to 80 mol%, or It may contain 55-80 mol %, or 60-80 mol %, or 50-75 mol %, or 55-75 mol %, or 60-75 mol %, or 65-75 mol % of ethylene glycol residues.

[0060] In one embodiment, the diol component of the polyester compositions useful in the present disclosure is up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, also up to 16 mol%, or up to 15 mol %, or up to 14 mol %, or up to 13 mol %, or up to 12 mol %, or up to 11 mol %, or up to 10 mol %, or up to 9 mol %, or up to 8 mol %, or up to 7 mol %, or up to 6 mol %, or up to 5 mol %, or up to 4 mol %, or up to 3 mol %, or up to 2 mol %, or up to 1 mol % of one or more modified diols (This modified diol is defined as a diol that is not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In certain embodiments, polyesters useful in the present disclosure may contain 10 mol % or less of one or more modified diols. In certain embodiments, polyesters useful in this disclosure may contain 5 mol % or less of one or more modified diols. In certain embodiments, polyesters useful in this disclosure may contain 3 mol % or less of one or more modified diols. In another embodiment, polyesters useful in this disclosure may contain 0 mole % modified diols. However, since some other diol residues may be generated in situ, the amount of residues generated in situ may also be considered an embodiment of the present disclosure.

[0061] In some embodiments, the modified diols used in the polyesters defined herein, when used, contain from 2 to 16 carbon atoms. Examples of modified diols include, but are not limited to, 1,2-propanediol, 1,3-propanediol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p- Xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and mixtures thereof. In one embodiment isosorbide is the modified diol. In another embodiment, modified diols include, but are not limited to, at least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, 1,3-propanediol and/or 1,4-butanediol may be excluded. When 1,4- or 1,3-butanediol is used, in one embodiment more than 4 mol % or more than 5 mol % may be provided. In one embodiment, the at least one modified diol is 1,4-butanediol present in an amount of 5-25 mole %.

[0062] In one embodiment, there is further provided a shrink film comprising a polyester composition comprising the following: 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component being 100 mole percent; present in an amount of 0.01 to about 10 mol %; diethylene glycol residues present in an amount of 2 to 9 mol %; neopentyl glycol residues present in an amount of 5 to 30 mol %; and ethylene glycol residues. The groups are present in amounts greater than or equal to 60 mol %.

[0063] In some embodiments, polyesters according to the present disclosure have 0 to 10 mol%, such as 0.01 to 5 mol%, 0.01 to 1 mol%, based on the total mol% of either diol or diacid residues. mol %, 0.05-5 mol %, 0.05-1 mol %, or 0.1-0.7 mol % of three or more carboxyl substituents, hydroxyl substituents, or combinations thereof, respectively; It may contain one or more branching monomer residues, also referred to herein as branching agents. In certain embodiments, a branching monomer or branching agent may be added before and/or during and/or after polymerization of the polyester. In some embodiments, the polyesters thus useful in this disclosure may be linear or branched.

[0064] Examples of branching monomers include, but are not limited to, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerin, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and polyfunctional acids or polyfunctional alcohols such as In one embodiment, the branched monomer residue is trimellitic anhydride, pyromellitic dianhydride, glycerin, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid. It may contain 0.1 to 0.7 mol % of one or more residues selected from at least one of them. The branching monomer may be added to the polyester reaction mixture or mixed with the polyester in the form of a concentrate, as described, for example, in U.S. Pat. The disclosure is incorporated herein by reference.

[0065] Polyesters useful in the present disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional isocyanates (including but not limited to difunctional), multifunctional epoxides such as epoxidized novolacs, and phenoxy resins. In certain embodiments, chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during a conversion process such as injection molding or extrusion.

[0066] The amount of chain extender used may vary depending on the particular monomer composition used and physical properties desired, but is generally 0.1% by weight based on the total weight of the polyester. ~10% by weight, such as 0.1% to 5% by weight.

[0067] The polyester compositions useful in the present disclosure, unless otherwise specified, have at least one of the intrinsic viscosity ranges described herein and the monomer range of the polyester composition described herein. It is contemplated that one may have a range of at least one of the The polyester compositions useful herein also have at least one range of the Tg ranges described herein and of the monomer ranges of the polyester composition described herein, unless otherwise specified. It is contemplated that there may be at least one range. Polyester compositions useful in the present disclosure also have at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein, unless otherwise specified. , and may have at least one range of the monomer ranges of the polyester compositions described herein.

[0068] In an embodiment of the present disclosure, the polyesters useful in the present disclosure have the following measured in 60/40 (wt/wt) phenol/tetrachloroethane at 25°C and a concentration of 0.25 g/50 mL. It may exhibit at least one of the intrinsic viscosity values: 0.50-1.2 dL/g; 0.50-1.0 dL/g; 0.50-0.90 dL/g; 0.55-0.80 dL/g; 0.60-0.80 dL/g; 0.65-0.80 dL/g; 0.70-0.80 dL/g; 0.50-0 0.55-0.75 dL/g; or 0.60-0.75 dL/g.

[0069] The glass transition temperature (Tg) of the polyester is measured using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C/min.
[0070] In certain embodiments, the oriented or shrink film of the present disclosure comprises a polyester/polyester composition having a polyester Tg of 60-80°C, 70-80°C, 65-80°C, or 65-75°C. include. In certain embodiments, these Tg ranges can be met with or without at least one plasticizer added during polymerization.

[0071] In embodiments of the present disclosure, certain oriented and/or shrinkable films comprising polyesters and/or polyester compositions useful in the present disclosure exhibit all of the following properties: excellent stretch, controlled specific toughness, specific intrinsic viscosity, specific glass transition temperature (Tg), specific strain-induced crystalline melting point, specific flexural modulus, specific density, specific tensile modulus, specific surface tension , excellent melt viscosity, excellent clarity, and excellent color.

[0072] In one embodiment, certain polyester compositions useful in this disclosure may be visually clear. The term "visually clear" is defined herein as the apparent absence of haziness, haze, and/or turbidity upon visual inspection.

[0073] The polyester portion of the polyester compositions useful in the present disclosure is made by methods known from the literature, such as in homogeneous solution, by transesterification in the melt, and by two-phase interface. may Suitable methods include, but are not limited to, one or more dicarboxylic acids with one or more diols at a temperature of 100° C. to 315° C. and a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. The process of making it react is mentioned. For methods of making polyesters, see US Pat. No. 3,772,405, the disclosure of which method is incorporated herein by reference.

[0074] Polyesters are generally prepared by gradually increasing the temperature to about 225°C to 310°C during condensation in an inert atmosphere to condense the dicarboxylic acid or dicarboxylic acid ester with the diol in the presence of a catalyst. and the second half of the condensation may be prepared by low pressure condensation as described in more detail in US Pat. No. 2,720,507, which is incorporated herein by reference.

[0075] In some embodiments, during the manufacturing process of the polyesters useful in this disclosure, certain chemicals that color the polymer may be added to melts containing toners or dyes. In one embodiment, a bluing toner is added to the melt to lower the b ^* of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toners and/or pigments. Red toners and/or pigments may also be used to adjust the a ^* tone. Organic toners, such as the toners described in US Pat. Nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entireties, such as blue and red organic toners, may also be used. Organic toners may be supplied as premixed compositions. The pre-mix composition may be a neat blend of the red and blue compounds, or the composition may be pre-dissolved or slurried in one of the raw materials of the polyester, such as ethylene glycol.

[0076] The total amount of toner components added depends on the amount of inherent yellow color in the base polyester and the efficacy of the toner. In one embodiment, mixed organic toner components may be used at a maximum concentration of about 15 ppm and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of bluing additive may range from 0.5 to 10 ppm. In one embodiment, toner may be added to the esterification reaction zone or the polycondensation reaction zone. Preferably, the toner is added to the esterification reaction zone or in the early stages of the polycondensation zone, such as the prepolymerization reactor.

[0077] The present disclosure further relates to polymer blends. In one embodiment, the polymer mixture comprises
(a) 5 to 95 weight percent of the polyester composition of the present disclosure as described herein; and (b) 5 to 95 weight percent of at least one polymer component.

[0078] Suitable examples of polymer components include, but are not limited to, nylon; polyesters different from those described herein; polyamides such as ZYTEL® from DuPont; polystyrene; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; polymethyl methacrylate; acrylic copolymers; dimethylphenylene oxide) or polyphenylene oxide/polystyrene blends such as NORYL 1000® (a mixture of poly(2,6-dimethylphenylene oxide) and polystyrene resin from General Electric); polyphenylene sulfide; polyphenylene sulfide polysulfones; polysulfone ethers; and polyether ketones of aromatic dihydroxy compounds; or mixtures of any of the foregoing polymers. In one embodiment, aliphatic-aromatic polyesters may be excluded from polyester compositions useful in this disclosure. The following polyesters that can be blended to make the polyester compositions of the present disclosure may be excluded as polymer components used in additional blends if the blend exceeds the compositional range of the present disclosure: polyethylene terephthalate (PET), glycol-modified PET (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), polycyclohexylene dimethylene terephthalate (PCT), acid-modified polycyclohexylene dimethylene terephthalate (PCTA), polybutylene terephthalate, and / or diethylene glycol modified PET (EASTOBOND ^™ copolyester).

[0079] The mixture may be prepared by conventional processing techniques known in the art such as melt blending or solution blending.
[0080] In some embodiments, the polyester compositions and polymer blend compositions also include, but are not limited to, colorants, toners, dyes, release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, UV Stabilizers, such as stabilizers and heat stabilizers, and/or common additives such as their reaction products, fillers, and impact modifiers, at 0.01 to 25% by weight of the total composition. It's okay. Examples of commercially available impact modifiers include, but are not limited to, impact modifiers of ethylene/propylene terpolymers, functionalized polyolefins such as methyl acrylate and/or glycidyl methacrylate, and styrenic block copolymers. and various acrylic core/shell impact modifiers. Residues of those additives are also considered part of the polyester composition.

[0081] Reinforcing materials may be added to the compositions useful in the present disclosure. Reinforcing materials may include, but are not limited to, carbon fibers, silicates, mica, clays, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, and polymeric fibers, and combinations thereof. good. In one embodiment, reinforcing materials include glass such as fibrous glass, glass and talc, glass and mica, and glass and polymeric fiber mixtures.

[0082] In one embodiment, films and shrink films according to the present disclosure may comprise 0.01 to 10% by weight polyester plasticizer. In one embodiment, the shrink film may contain 0.1-5% by weight polyester plasticizer. Generally, the shrink film may contain 90-99.99% by weight of copolyester. In certain embodiments, the shrink film may comprise 95-99.9% by weight copolyester.

[0083] In one aspect, the present disclosure relates to shrink films and molded articles of the present disclosure comprising polyester compositions and/or polymer blends useful in the present disclosure. Methods of forming polyester compositions and/or mixtures into films and/or sheets are well known in the art. Examples of films and/or sheets useful in the present disclosure include, but are not limited to, extruded films and/or sheets, compression molded films, calendered films and/or sheets, solution cast films and/or sheets. In one aspect, film and/or sheet making methods useful for making the shrink films of the present disclosure include, but are not limited to, extrusion, compression molding, rolling, and solution casting.

[0084] In one embodiment, the polyester compositions useful in this disclosure are made into films using any method known in the art for making films from polyesters, such as solution casting, extrusion, compression molding, or rolling. manufactured to

[0085] In one embodiment, the as-formed film is subsequently oriented in one or more directions (eg, as a uniaxially and/or biaxially oriented film). This orientation of the film can be performed by any method known in the art using standard orientation conditions. For example, oriented films of the present disclosure may be made from films, such as extruded, cast, or calendered films, having a thickness of about 100-400 μm, the oriented films having a thickness between Tg and Tg+55°C, or 70°C. It may be oriented in a ratio of 5:1 to 3:1 at a temperature of ~125°C, such as in a ratio of 5:1 or 3:1 at a temperature of thickness. In one embodiment, orientation of the initial preshrunk film may be performed in a tenter frame according to these orientation conditions.

[0086] The shrink films of the present disclosure may have a shrink onset temperature of about 55 to about 80°C, or about 55 to about 75°C, or about 55 to about 70°C. The shrinkage initiation temperature is the temperature at which the initiation of shrinkage occurs.

[0087] In certain embodiments, the polyester compositions useful in the present disclosure are 1.6 g/cc or less, or 1.5 g/cc or less, or 1.4 g/cc or less, or 1.1 g/cc to 1 5 g/cc, or from 1.2 g/cc to 1.4 g/cc, or from 1.2 g/cc to 1.35 g/cc.

[0088] In one embodiment, many small voids or holes are introduced into the film or molded article to reduce the density of the film. This process is called "voiding" and is sometimes called "cavitating" or "microvoiding". These pores are formed from about 1 to about 50% by weight of small organic particles or inorganic particles (including glass microspheres) or "inclusions" (also known in the art as "pore-forming" or "cavitation" agents). ) is incorporated into the matrix polymer and stretched in at least one direction to orient the polymer. During stretching, small cavities or pores are formed around the pore former. When voids are introduced into a polymer film, the resulting voided film is not only less dense than nonvoided films, but also becomes opaque and presents a paper-like surface. This surface also has the advantage of improving printability, ie, the surface can accept more ink at a substantially greater volume than a non-voided film. 4,582,752; 4,632,869; 4,770,931; 5,176,954; 5,435,955; 5,843,578; 6,720,085; U.S. Patent Application Publication Nos. 2001/0036545; 2003/0068453; 2003/0165671; 2003/0170427; 0 581 970 B1; European Patent Application Publication No. 0 214 859 A2.

[0089] In certain embodiments, the as-extruded film is oriented during stretching. The oriented or shrinkable films of the present disclosure can be made from films having any thickness depending on the desired end use. In one embodiment, the desired conditions are as oriented and/or shrinkable films for applications such as photographic films that can adhere to substrates such as labels, paper, and/or for other applications where they are useful. Therefore, it is possible to print with ink. It may be desirable to coextrude the polyesters useful in this disclosure with another polymer, such as PET, so that the films can be used as oriented and/or shrink films in this disclosure. One advantage of performing the latter coextrusion is that a tie layer may not be required in some embodiments.

[0090] In one embodiment, the uniaxially and biaxially oriented films of the present disclosure may be made from films having a thickness of about 100-400 μm, such as extruded, cast, or calendered films, which are , the film may be stretched at a temperature of Tg to Tg+55° C. at a ratio of 6.5:1 to 3:1, and may be stretched to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial as-extruded film may be performed in a tenter according to these orientation conditions. Shrink films of the present disclosure can be made from oriented films of the present disclosure.

[0091] In certain embodiments, the shrink films of the present disclosure shrink gently with little or no wrinkling. In certain embodiments, the shrink films of the present disclosure have a shrinkage of 40% or less in the transverse direction for each 5°C temperature increase.

[0092] In certain embodiments of the present disclosure, the shrink films of the present disclosure exhibit a shrinkage of 10% or less, or 5% or less, or 3% or less, or 2% or less in the machine direction when immersed in water at 65°C for 10 seconds. % or no shrinkage. In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage of -10% to 10%, -5% to 5%, or -5% to -5% in the machine direction when immersed in water at 65°C for 10 seconds. 3%, or -5% to 2%, or -4% to 4%, or -3% to 4%, or -2% to 4%, or -2% to 2.5%, or -2% to It has a shrinkage of 2%, or 0-2%, or no shrinkage. Here, negative shrinkage in the machine direction indicates expansion in the machine direction. A positive shrinkage in the machine direction indicates shrinkage in the machine direction.

[0093] In certain embodiments of the present disclosure, the shrink films of the present disclosure shrink 50% or more, or 60% or more, or 70% or more in the principal shrink direction when immersed in water at 95°C for 10 seconds. have a rate.

[0094] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a shrinkage of 50-90% in the main shrink direction when immersed in water at 95°C for 10 seconds, and It has a shrinkage of 10% or less or -10% to 10%.

[0095] In one embodiment, the polyesters useful in this disclosure are made into films using any method known in the art for making films from polyesters, such as solution casting, extrusion, compression molding, or rolling. be made. The as-extruded (or as-formed) film is then oriented in one or more directions (eg, uniaxially and/or biaxially oriented film). This orientation of the film may be performed by any method known in the art using standard orientation conditions. For example, a uniaxially oriented film of the present disclosure may be made from a film, such as an extruded, cast, or calendered film, having a thickness of about 100-400 μm, the film having a thickness between Tg of the film and Tg+55°C. It may be stretched at a temperature ratio of 6.5:1 to 3:1 and may be stretched to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial as-extruded film may be performed in a tenter according to these orientation conditions.

[0096] In certain embodiments, the shrink films of the present disclosure have a shrinkage of 40% or less in the transverse direction for each 5°C temperature increase.
[0097] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink onset temperature of from about 55 to about 80°C, or from about 55 to about 75°C, or from about 55 to about 70°C. good. The shrinkage initiation temperature is the temperature at which the initiation of shrinkage occurs.

[0098] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink initiation temperature of from about 55°C to about 70°C.
[0099] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a percent strain to break greater than 200% at a draw rate of 500 mm/min in the direction perpendicular to the primary shrink direction according to ASTM Method D882. good too.

[00100] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a percent strain to break greater than 300% at a draw rate of 500 mm/min in the direction perpendicular to the primary shrink direction according to ASTM Method D882. good too.

[00101] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a tensile stress at break (stress at break) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa, measured according to ASTM Method D882. may have

[00102] In certain embodiments of the present disclosure, the shrink films of the present disclosure exhibit a shrink force of 4 to 18 MPa, or 4 to 15 MPa, as measured by ISO Method 14616, depending on stretching conditions and desired end use. may have. For example, certain labels made for plastic bottles may have a shrinkage force of 4-8 MPa, measured by ISO Method 14616 using a LabThink Shrink Force Tester at 80° C.; Certain labels made for may have a shrinkage force of 10-14 Mpa.

[00103] In one embodiment of the present disclosure, the polyester composition is formed by reacting monomers by known methods for making polyesters, typically referred to as reactor grade compositions. good too.

[00104] In one embodiment of the present disclosure, the polyester composition of the present disclosure comprises polyethylene terephthalate (PET), glycol-modified PET (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), polycyclohexylene dimethylene terephthalate (PCT), acid-modified polycyclohexylene dimethylene terephthalate (PCTA), polybutylene terephthalate, and/or diethylene glycol modified PET (EASTOBOND ^™ copolyester) to achieve the monomer range of these compositions. It may be produced by mixing.

[00105] In certain embodiments, the polyester compositions and polymer blend compositions contain colorants, toners, dyes, release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, UV stabilizers, including but not limited to and stabilizers, such as heat stabilizers, and/or common additives such as their reaction products, fillers, and impact modifiers, in an amount of 0.01 to 25% by weight of the total composition. It's okay. Examples of commercially available impact modifiers include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as olefins containing methyl acrylate and/or glycidyl methacrylate, styrenic block copolymers. Included are impact modifiers and various acrylic core/shell impact modifiers. Residues of those additives are also considered part of the polyester composition.

[00106] Reinforcing materials may be added to the polyester compositions useful in this disclosure. Reinforcing materials may include, but are not limited to, carbon fibers, silicates, mica, clays, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, and polymeric fibers, and combinations thereof. good. In one embodiment, reinforcing materials include glass such as fibrous glass, glass and talc, glass and mica, and glass and polymeric fiber mixtures.

[00107] Shaped articles that consist of, or include, but not consist of, shrink films can also be made from any of the polyester compositions disclosed herein and are within the scope of the present disclosure. include.

[00108] Generally, shrink films according to the present disclosure may include 0.01 to 10% by weight polyester plasticizer. In one embodiment, the shrink film may contain 0.1-5% by weight polyester plasticizer. Generally, the shrink film may contain 90-99.99% by weight of copolyester. Generally, the shrink film may contain 95-99.9% by weight of copolyester.

[00109] In one embodiment, having a pre-oriented thickness of about 100 to 400 μm, followed by about 20 to about 80 μm at a temperature of Tg to Tg + 55°C and a ratio of 6.5:1 to 3:1. When oriented on a tenter to thickness, the shrink films of the present disclosure exhibit the following properties:
(1) When immersed in water at 95°C for 10 seconds, it shrinks by more than 60% (or more than 70%) in the main shrinkage direction or transverse direction and 10% or less (or -5% or more) in the machine direction. 4%);
(2) a shrinkage onset temperature of about 55°C to about 70°C;
(3) greater than 200%, or from 200 to 600%, or from 200 to 500%, or from 226 to 449%, or from 250 to 500 mm/min in the transverse direction, machine direction, or both directions according to ASTM Method D882; 455% breaking strain rate;
(4) shrinkage by 40% or less for every 5°C temperature increase; and/or (5) a strain-induced crystal melting point greater than 200°C. Any combination of these properties, or all of these properties, may be present in the shrink films of the present disclosure. The shrink films of the present disclosure may have a combination of two or more of the shrink film properties described above. The shrink films of the present disclosure may have combinations of three or more of the shrink film properties described above. The shrink films of the present disclosure may have combinations of four or more of the shrink film properties described above. In certain embodiments, properties (1)-(2) are present. In certain embodiments, properties (1)-(5) are present. In certain embodiments, properties such as (1)-(3) are present.

[00110] Shrinkage herein refers to tenter tenter based on initial as-produced films with a thickness of about 20-80 μm oriented at . In one embodiment, the shrink properties of the oriented film used to make the shrink films of the present disclosure were not altered by heat treating the film at a temperature higher than the temperature at which the film was oriented.

[00111] The shape of the films useful in making the oriented or shrink films of this disclosure is not subject to any limitations. For example, the shape may be a flat film or a tubular shaped film. To produce shrink films useful in this disclosure, the polyester is first formed into a flat film and then "uniaxially oriented," which means orienting the polyester film in one direction. The film may also be "biaxially oriented," meaning that the polyester film is oriented in two different directions, e.g., the film is stretched in both the machine direction and a direction different from the machine direction. . Typically the two directions are substantially perpendicular, but this is not always the case. For example, in one embodiment, the two directions are the longitudinal or machine direction (“MD”) of the film (the direction in which the film is manufactured on the film making machine) and the transverse direction (“TD”) of the film (in the MD of the film). perpendicular direction). Biaxially oriented films may be oriented sequentially, oriented simultaneously, or oriented by some combination of stretching simultaneously and sequentially.

[00112] The film may be oriented by any conventional method such as roll stretching, long gap stretching, tenter stretching, and tubular stretching. Any of these methods may be used to carry out continuous biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof. Using biaxial stretching as described above, stretching in the machine and transverse directions may be carried out simultaneously. Stretching can also be done first in one direction and then in the other direction, effectively resulting in biaxial stretching. In one embodiment, stretching of the films is carried out by preheating the films from 5° C. to 80° C. above their glass transition temperature (Tg). In one embodiment, the films may be preheated at a temperature between 10°C and 30°C above their Tg. In one embodiment, the draw speed is 5 to 20 inches (12.7 to 50.8 cm) per second. The film may then be oriented, for example, from 2 to 6 times its original dimensions in either the machine direction, transverse direction, or both directions. The film may be oriented as a single film layer or may be coextruded with another polyester such as PET (polyethylene terephthalate) as a multilayer film and then oriented.

[00113] In one embodiment, the present disclosure includes articles of manufacture or molded comprising the shrink film of any of the shrink film embodiments of the present disclosure. In another embodiment, the present disclosure includes an article of manufacture or molded article comprising an oriented film of any of the oriented film embodiments of the present disclosure.

[00114] In certain embodiments, the present disclosure includes, but is not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and/or industrial products or other applications. including. In one embodiment, the present disclosure is applied to, but not limited to, containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, hot-fill containers, and/or industrial products or other uses. Including oriented films.

[00115] In certain embodiments of the present disclosure, the shrink films of the present disclosure may be formed into labels or sleeves. The label or sleeve may then be applied to the wall of the container, the article of manufacture such as the battery, or onto the sheet or film.

[00116] Oriented or shrinkable films of the present disclosure can be applied to shaped articles such as sheets, films, tubes, or bottles and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyesters, polylactic acid (PLA) are frequently used in the production of shrink labels for plastic beverage or food containers. For example, the shrink films of the present disclosure can be used in many packaging applications in which the shrink films applied to molded articles exhibit excellent printability, high opacity, high shrink force, excellent texture, and high stiffness. and other characteristics.

[00117] The combination of improved shrink properties and improved toughness allows for application to, but not limited to, containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and/or industrial products or other applications. It should provide new commercial options such as shrink films.

[00118] In one aspect of the present disclosure, the disclosed polyester compositions are useful as thermoformable films or sheets and/or thermoformable films or sheets. The present disclosure is also directed to articles of manufacture incorporating the thermoformed films and/or sheets of the present disclosure. In one embodiment, the polyester compositions of the present disclosure are useful as films and sheets that are readily formed into molded articles or formed articles. In one embodiment, the films and/or sheets of the present disclosure can be processed into shaped articles or parts by thermoforming. The polyester compositions of the present disclosure can be used in various molding and extrusion applications.

[00119] Further, in one embodiment, the polyester compositions and polyester blends useful in the thermoformable sheets of the present disclosure also include, but are not limited to, colorants, mold release agents, flame retardants, plasticizers, nucleating agents, UV stabilizing agents, Stabilizers such as additives and heat stabilizers, fillers, and common additives such as impact modifiers may be included at 0.1 to 25% by weight of the total composition.

[00120] In one embodiment, a reinforcing material may be included in a thermoformed film or sheet comprising the polyester composition of the present disclosure. For example, suitable reinforcing materials may include carbon fibers, silicates, mica, clays, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymeric fibers, and combinations thereof.

[00121] In one embodiment, the thermoformed film or sheet of the present disclosure is a multilayer film or sheet. In one embodiment, at least one layer of the multilayer film or sheet is a foam layer or a foamed polymer or polyester layer.

[00122] One aspect of the present disclosure is a method of manufacturing formed or molded parts and articles using thermoforming. Any thermoforming technique or process known to one of ordinary skill in the art can be used to produce the shaped or molded articles of the present disclosure.

[00123] In one embodiment, the thermoforming process is described, for example, in "Technology of Thermoforming" (Throne, James; Hanser Publishers; 1996; pp. 16-29, incorporated herein by reference). It can be done in several ways, as taught in Ref. In some embodiments, the process is a male mold thermoforming process in which gas pressure or air pressure is applied to the softened sheet, then the sheet is stretched and drawn out like a bubble, and the male mold is placed inside the bubble. be. A vacuum is then applied to pull the part further and conform to the surface of the male mold. The thermoforming process primarily performs biaxial stretching/orientation in one step when gas pressure or air pressure is applied to the softened sheet. The molding process is then completed using vacuum and male molds to fix the orientation within the sheet for a good balance of physical and appearance properties. In other embodiments, the process applies a vacuum or physical plug to the heat-softened sheet, stretches and pulls the sheet to near final part dimensions, and then applies positive air pressure from the inside or further outside pressure from the outside. A female mold thermoforming process that draws a sheet by pulling a vacuum to fit it into an outer female mold, fixing the orientation within the polymer and forming the sheet into an article.

[00124] In some embodiments, bubble creation may be further formed utilizing a plug aid, followed by sheeting and molding the ascending male mold, and then the corners. And the shelf guide part etc. are drawn into the mold by applying a vacuum. In some embodiments, after removal from the mold, the formed part or article may be cut, punched, and corners trimmed as necessary.

[00125] In other embodiments, thermoforming involves heating a film or sheet of the polyester composition of the present disclosure to a temperature sufficient to allow it to deform, and then the heated film or sheet is vacuum-assisted, The process of conforming to the contour of the mold by means such as pneumatic assistance and matched mold assistance. In another embodiment, the heated film or sheet is placed in a mold and forced to conform to the contours of the mold, such as by applying air pressure, using a vacuum plug aid, or using a matched mold. be done. In some embodiments, thermoforming is used to produce thin-walled articles.

[00126] In one embodiment, the thermoforming process forms the film or sheet into the desired shape by forcing a male mold into the heated film or sheet. In this embodiment, thermoforming involves having a male mold of the article supported between evacuated surfaces or tables. In this embodiment, heat is directed at the film or sheet from an external heat source such as a hot air blower, heat lamp, or other radiant heat source. In this embodiment, the film or sheet is heated to its softening point. In this embodiment, a vacuum is then applied to the table, under the table, and around the mold to draw the thermally softened film or sheet toward the table and bring the softened film or sheet into contact with the mold surface. Deploy. In this embodiment, the vacuum draws the softened film or sheet into intimate contact with and conform to the contours of the mold surface. This gives the film or sheet the shape of the mold. In these embodiments, after the film or sheet has cooled, the sheet can be cured and the resulting article or part removed from the mold.

[00127] In one embodiment, the thermoforming process comprises forming a film or sheet from the polyester composition of the present disclosure; heating the film or sheet until it softens and placing the sheet on a mold; drawing the formed film or sheet to a heated mold surface; cooling the film or sheet; then removing the formed article or part from the mold cavity, or optionally partially removing the film or sheet. Heat setting the formed film or sheet by maintaining the film or sheet in contact with the heated mold for a time sufficient to crystallize to .

[00128] In one embodiment, the thermoforming process comprises forming a sheet from the polyester composition of the present disclosure; heating the film or sheet to a temperature equal to or above the Tg of the polyester; applying pressure, vacuum, and/or physical pressure to draw the film or sheet to approximately the final part dimensions; conforming the film or sheet to the shape of the mold by vacuum or pressure; cooling to a temperature below; and then removing the thermoformed article or part from the mold.

[00129] Films or sheets for use in the thermoforming process may be made by any conventional method known to those skilled in the art. In one embodiment, the film or sheet is formed by extrusion. In one embodiment, the film or sheet is formed by rolling. In one embodiment, the film or sheet is heated to a temperature above the Tg of the polyester during the thermoforming process. In one embodiment, the temperature is from about 10° C. to about 60° C. above the Tg of the polyester. In one embodiment, it is necessary to heat the film or sheet prior to placing it on the thermoforming mold in order to achieve shorter molding times. In one embodiment, the sheet should be heated above its Tg and below a temperature at which the sheet would sag excessively during placement over the mold cavity. In one embodiment, the formed film or sheet is allowed to cool below the Tg of the polyester prior to removal from the mold. In one embodiment, the thermoforming method may include vacuum aids, air aids, mechanical plug aids, or matched mold. In some embodiments, the mold is heated to a temperature above the Tg of the film or sheet. The selection of the optimum mold temperature depends on the mold of the thermoforming equipment, the structure and wall thickness of the article to be formed, and other factors.

[00130] In some embodiments, the heated film or sheet is stretched by generating and introducing a vacuum.
[00131] In one embodiment, heat setting is a process that thermally induces partial crystallization of a polyester film or sheet without the presence of any perceptible orientation. In one embodiment, heat setting maintains contact between the film or sheet and the heated mold surface for a time sufficient to achieve a level of crystallinity that imparts suitable physical properties to the finished part. achieved by In one embodiment, the level of crystallinity should be from about 10 to about 30%.

[00132] In one embodiment, the heat-set part may be removed from the mold cavity by known means for removal. For example, in one embodiment, blowback is used, which involves introducing compressed air to break the vacuum established between the mold and the formed film or sheet. In some embodiments, the excess portion of the formed article or part is then cut away and the waste is crushed for recycling.

[00133] In some embodiments, the addition of a nucleating agent provides faster crystallization during thermoforming and thus provides faster forming. In one embodiment, a nucleating agent such as a fine particle size inorganic or organic material may be used. For example, in one embodiment, suitable nucleating agents include talc, titanium dioxide, calcium carbonate, and immiscible or crosslinked polymers. In one embodiment, nucleating agents may be used in amounts that vary from about 0.01% to about 20% by weight of the article. In one embodiment, other conventional additives such as pigments, dyes, plasticizers, crack inhibitors, and stabilizers may be used as needed for thermoforming. In some embodiments, anti-cracking agents improve impact strength and nucleating agents provide faster crystallization. In some embodiments, crystallization is necessary to achieve high temperature stability.

[00134] In one embodiment, a foamed polyester film or sheet is prepared by foaming a polyester composition of the present disclosure with a chemical and/or physical blowing agent, extruding the foamed polyester into a sheet or film, and forming a foamed polyester film or sheet. is made by thermoforming. Additives may be added to the polyester prior to foaming to improve the properties of the foamed polyester film. Examples of such additives include slip agents, antiblocking agents, plasticizers, optical brighteners, and UV inhibitors. In one embodiment, the foamed polyester film may be an extrusion or laminate that has been coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the covering material should be a printed surface that provides product labeling, rather than the foamed film itself.

[00135] The compositions of the present disclosure are useful as formed or molded plastic parts or as solid plastic articles. The compositions of the present disclosure are useful as thermoformed parts or articles. This composition is suitable for use in any application where a clear, rigid plastic is required. Examples of this part include disposable knives, forks, spoons, plates, cups, straws, as well as spectacle frames, toothbrush handles, toys, car accessories, tool handles, camera parts, electronics parts, razor parts, ink pens. Shafts, disposable syringes, bottles, and the like. In one embodiment, the compositions of this disclosure are useful as plastics, films, fibers, and sheets. In one embodiment, the composition is used in bottles, bottle caps, spectacle frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic enclosures, electronic cases, computer monitors, printers, Manufactures keyboards, tubes, automotive parts, automotive interior parts, automotive accessories, signs, thermoformed letters, wallboards, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household items. It is useful as a plastic to In another embodiment, the compositions of the present disclosure are used in films, sheets, fibers, molded articles, molded articles, molded parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, shipping containers. , packaging, bottles, bottle caps, spectacle frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf partitions, furniture parts, electronic device casings, electronic device cases, computer monitors, printers, keyboards, tubes , Toothbrush handles, Automotive parts, Automotive interior parts, Automotive accessories, Signboards, Outdoor signboards, Skylights, Multi-wall layer films, Multi-layer films, Thermal insulation parts, Thermal insulation articles, Thermal insulation containers, Thermoforming characters, Wallboards, Toys, Toys Components, trays, food trays, dental trays, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles and household items, health care products, commercial food supply products, boxes, graphic arts films, Plastic films for plastic glass laminates, point-of-purchase displays, skylights, smoke vents, laminated cards, fencing, glazing, partitions, ceiling tiles, lighting, mechanical protection plates, graphic arts, lenses , extrusion laminated sheets or films, decorative laminates, office furniture, face shields, medical packaging, display shelf sign holders, and shelf price holders.

[00136] Thermoforming or thermoformable compositions of the present disclosure are useful for forming films, formed articles, formed parts, molded articles, molded parts, and sheets. The method of making the thermoforming or thermoformable composition into films, formed articles, formed parts, molded articles, molded parts, and sheets may be according to any method known in the art. Examples of formed articles include, but are not limited to, commercial food supplies such as medical devices, medical packaging, healthcare products, trays, containers, food plates, tumblers, bins, bottles, food processors, mixing bowls, and the like. Products include household items, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[00137] The present disclosure further relates to articles of manufacture comprising films and/or sheets comprising the polyester compositions described herein. In some embodiments, films and/or sheets of the present disclosure may be of any thickness required for the intended application.

[00138] The present disclosure further relates to the films and/or sheets described herein. Methods of forming the polyester composition into films and/or sheets include any methods known in the art. Examples of films and/or sheets of the present disclosure include, but are not limited to, extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, and solution cast films and/or sheets. Films and/or sheets are included. Methods of making films and/or sheets include, but are not limited to, extrusion, rolling, compression molding, wet block processing, dry block processing, and solution casting.

[00139] The present disclosure further relates to formed or molded articles described herein. Methods of forming the polyester composition into shaped or molded articles include any methods known in the art. Examples of formed or molded articles of the present disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extruded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. is mentioned. Methods of making shaped articles include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. The process of the present disclosure may include any thermoforming process known in the art. The process of the present disclosure may include any blow molding process known in the art including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

[00140] This disclosure includes any injection blow molding manufacturing process known in the art. A typical, non-limiting description of an injection blow molding (IBM) manufacturing process includes the steps of 1) melting the composition in a reciprocating screw extruder, 2) injecting the molten composition into an injection mold, forming a partially cooled tube closed at one end (i.e., the preform); 3) moving the preform into a blow mold having the desired final shape around the preform; 4) blowing air through the preform to stretch and expand the preform to fill the mold; 5) cooling the molded article; and 6). It includes removing the article from the mold.

[00141] This disclosure includes any injection stretch blow molding manufacturing process known in the art. A typical, non-limiting description of an injection stretch blow molding (ISBM) manufacturing process includes: 1) melting the composition in a reciprocating screw extruder; 3) moving the preform into a blow mold having the desired final shape around the preform; , closing the blow mold around the preform; 4) stretching the preform using internal stretching rods, blowing air into the preform, stretching and expanding the preform to close the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[00142] The present disclosure includes any extrusion blow molding manufacturing process known in the art. A typical, non-limiting description of an extrusion blow molding manufacturing process includes the steps of: 1) melting the composition in an extruder; 2) extruding the molten composition through a die to form a tube (i.e., parison) of molten polymer. 3) fixing a mold having the desired final shape around the parison; 4) blowing air into the parison to stretch and expand the extrudate to fill the mold; 6) removing the article from the mold; and 7) removing excess plastic (commonly referred to as flash) from the article.

[00143] In another aspect of the present disclosure, it has been found that the polyester resins of the present disclosure can be made from recycled copolyesters and/or recycled polyesters.

[00144] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); additional terephthalic acid (TPA) and ethylene glycol (EG) to a total glycol:TPA molar ratio of 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer. adding at;
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in a second reaction zone, the first esterification product and optionally additionally added glycol, optionally in the presence of an esterification catalyst and/or stabilizer, at least 200°C. further reacting at a melting temperature of to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone the second esterification product optionally reacting with a polycondensation catalyst and/or or polycondensing in the presence of a stabilizer to produce a polymerization product comprising a polyester.

[00145] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) terephthalic acid (TPA) or its ester and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; introducing the recycled polyester containing into the paste tank and stirring and heating at a maximum temperature of 150° C. to produce a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); add additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and Additional terephthalic acid (TPA) and ethylene glycol (EG) are added to give a glycol:TPA molar ratio of 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer. the step of
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in the second reaction zone additional glycols optionally comprising one or more of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT; Addition of additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer to a melt of at least 200°C further reacting the first esterification product at temperature to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, optionally in the presence of a polycondensation catalyst and/or stabilizer, a second polycondensing the esterification product of 2 to produce a polymerization product comprising a polyester.

[00146] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); add additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and Additional terephthalic acid (TPA) and ethylene glycol (EG) are added to give a glycol:TPA molar ratio of 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer. the step of
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in the second reaction zone additional glycols optionally comprising one or more of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT; Addition of additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer to a melt of at least 200°C further reacting the first esterification product at temperature to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, optionally recycled PET, recycled PETG, recycled Additional recycled polyester comprising one or more of PCT, recycled PCTA, or recycled PCTG is added to form a second, optionally in the presence of a polycondensation catalyst and/or stabilizer. polycondensing the esterified product to produce a polymerized product comprising a polyester.

[00147] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste bath, stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), into the first reaction zone for recycling; adding recycled polyester comprising one or more of PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally total glycol:TPA molar ratio adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the is 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer;
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 175° C. to produce a second reaction mixture comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in the second reaction zone additional glycols optionally comprising one or more of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT; Addition of additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer to a melt of at least 200°C further reacting the first esterification product at temperature to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, optionally recycled PET, recycled PETG, recycled Additional recycled polyester comprising one or more of PCT, recycled PCTA, or recycled PCTG is added to form a second, optionally in the presence of a polycondensation catalyst and/or stabilizer. polycondensing the esterified product to produce a polymerized product comprising a polyester.

[00148] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), into the first reaction zone for recycling; adding recycled polyester comprising one or more of PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally total glycol:TPA molar ratio adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the is 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer;
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) additional glycols and/or recycled PET, recycled PETG, recycled PCT, recycled PCTA comprising one or more of CHDM, NPG, or DEG in the second reaction zone; , or with the addition of additional recycled polyester comprising one or more of recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer at a melt temperature of at least 200°C. further reacting the esterification product of to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, optionally recycled PET, recycled PETG, recycled Additional recycled polyester comprising one or more of PCT, recycled PCTA, or recycled PCTG is added to form a second, optionally in the presence of a polycondensation catalyst and/or stabilizer. polycondensing the esterified product to produce a polymerized product comprising a polyester.

[00149] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally a total glycol:TPA molar ratio of 1:1 to 4. : adding terephthalic acid (TPA) and ethylene glycol (EG) to 1, optionally in the presence of an esterification catalyst and/or stabilizer;
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in the second reaction zone additional glycols optionally comprising one or more of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT; Addition of additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer to a melt of at least 200°C further reacting the first esterification product at temperature to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, recycled PET, recycled PETG, recycled PCT, recycled Additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, is added to form a second esterification product, optionally in the presence of a polycondensation catalyst and/or stabilizer. to produce a polymerization product comprising a polyester.

[00150] One embodiment of the present disclosure is a process for making a polyester composition from recycled polyester, the process comprising:
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to the first reaction zone;
(c) introducing into the first reaction zone at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); Recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG is added and optionally the total glycol:TPA molar ratio is 1:1 to 4:1. adding terephthalic acid (TPA) and ethylene glycol (EG), optionally in the presence of an esterification catalyst and/or stabilizer;
(d) reacting TPA and EG with at least one additional glycol in a first reaction zone at a melting temperature of at least 200° C. to produce a second reaction comprising oligomers and unreacted TPA, EG, and additional glycol; producing an esterification product of 1;
(e) delivering the first esterification product to a second reaction zone;
(f) in the second reaction zone additional glycols optionally comprising one or more of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT; Addition of additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer to a melt of at least 200°C further reacting the first esterification product at temperature to produce a second esterification product comprising a polyester oligomer;
(g) delivering the second esterification product to a third reaction zone; and (h) within the third reaction zone, recycled PET, recycled PETG, recycled PCT, recycled Additional recycled polyester comprising one or more of recycled PCTA, or recycled PCTG, is added to form a second esterification product, optionally in the presence of a polycondensation catalyst and/or stabilizer. to produce a polymerization product comprising a polyester.

[00151] In one embodiment, the recycled polyester and/or copolyester may be recovered as manufacturing waste or industrial waste or post-consumer recycling (PCR) waste. Typically, PCR or recycled waste is articles made from used and discarded polyester or copolyester. PET is now being recycled by mechanical methods and incorporated into new PET bottles and other PET articles as a mixture with virgin materials.

[00152] Copolyesters with recycled content and copolyesters made from recycled content contain dicarboxylic acid monomer residues, diol or glycol monomer residues, and repeat units. Thus, the term "monomeric residue" as used herein means a dicarboxylic acid, diol or glycol, or hydroxycarboxylic acid residue. As used herein, "repeat unit" means an organic structure having two monomeric residues linked through a carbonyloxy group. Copolyesters of the present disclosure contain acid residues (100 mol %) and glycol residues (100 mol %) reacted in substantially equal proportions such that the total number of moles of repeating units equals 100 mol %. contains. Thus, mole % given in this disclosure may be based on total moles of acid residues, total moles of glycol residues, or total moles of repeat units. For example, a copolyester containing 30 mol % of a monomer, which may be a dicarboxylic acid, glycol, or hydroxycarboxylic acid, based on total repeating units, the copolyester has 30 mol % of 100 mol % of total repeating units. It is meant to contain monomers. Therefore, there will be 30 moles of monomer residues for every 100 moles of repeat units. Similarly, a copolyester containing 30 mole % dicarboxylic acid monomers based on total acid residues means that the polyester contains 30 mole % dicarboxylic acid monomers out of 100 mole % total acid residues. . Thus, in this latter case, there will be 30 moles of dicarboxylic acid monomer residues for every 100 moles of acid residues.

[00153] As used herein, the term "polyester" includes both "homopolymers" and "homopolyesters" and "copolyesters" and includes at least one A synthetic polymer prepared by polycondensation of a diacid component of the species and at least one glycol component containing one or more difunctional hydroxyl compounds. As used herein, the term "copolyester" refers to the polycondensation of at least three different monomers, such as a dicarboxylic acid and two or more glycols, or in another example a diol and two or more different dicarboxylic acids. It is intended to mean polyesters formed from polycondensation. Typically the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as glycols and diols. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound is an aromatic nucleus with two hydroxy substituents, such as hydroquinone. good too. As used herein, the term "residue" means any organic structure incorporated into a polymer by a polycondensation reaction involving the corresponding monomer. Dicarboxylic acid residues may be derived from dicarboxylic acid monomers, or their associated acid halides, esters, salts, anhydrides, or mixtures thereof. For example, in one embodiment, the copolyesters of the present disclosure provide the diacid component as terephthalic acid or isophthalic acid.

[00154] The recycled polyester and/or copolyester may be repolymerized to copolyester using any polycondensation reaction conditions known in the art. They may be produced by continuous, semi-continuous, and batch modes of operation and may utilize various reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuously stirred tank, slurry, tubular, wiped film, falling film, or extruded reactors. As used herein, the term "continuous" means a process in which reactants are introduced and products are removed simultaneously in an uninterrupted manner. The process is beneficially operated as a continuous process for economic reasons and because staying in the reactor at high temperatures for too long can cause the copolyester to deteriorate in appearance. It is operated to produce polymer with excellent color tone.

[00155] The copolyesters of the present disclosure are prepared by procedures known to those skilled in the art. The reaction of the diol component and the dicarboxylic acid component may be carried out using conventional copolyester polymerization conditions. For example, when preparing a copolyester from an ester form of a dicarboxylic acid component by a transesterification reaction, the reaction process may involve two steps. In the first step, a diol component and a dicarboxylic acid component, such as terephthalic acid, are combined at an elevated temperature of about 150° C. to about 250° C. for about 0.5 to about 8 hours at about 0.0 kPa atmospheric pressure to about 0.0 kPa atmospheric pressure. React at pressures in the range of 414 kPa atmospheric pressure standard (60 pounds per square inch, "psig"). The temperature of the transesterification reaction ranges from about 180° C. to about 230° C. for about 1 hour to about 4 hours, and the pressure ranges from about 103 kPa atmospheric pressure (15 psig) to about 276 kPa atmospheric pressure (40 psig). is. The reaction product is then heated at a higher temperature and under reduced pressure to drive out the diol to form a copolyester, whereupon the diol readily volatilizes at these conditions and is driven out of the system.

[00156] This second step, the polycondensation step, is performed under higher vacuum and generally in the range of about 230°C to about 350°C, or about 250°C to about 310°C, or about 260°C to about 290°C. at a temperature of from about 0.1 to about 6 hours, or from about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization determined by the intrinsic viscosity is obtained. The polycondensation step may be carried out under reduced pressure ranging from about 400 torr to about 0.1 torr. Stirring or suitable conditions are used in both stages to ensure adequate heat transfer and surface regeneration of the reaction mixture and exclusion of water, excess glycol, or alcohol to facilitate reaction and polymerization. The reaction rate in both stages is increased by suitable catalysts such as alkoxytitanium compounds, alkali metal hydroxides and alcoholates, organic carboxylates, alkyltin compounds, metal oxides and the like. A three-step manufacturing procedure similar to that described in US Pat. No. 5,290,631 may also be used, especially when mixed monomer stocks of acids and esters are used.

[00157] To ensure complete reaction of the diol component and the dicarboxylic acid component by transesterification, using about 1.05 to about 2.5 moles of diol component per mole of dicarboxylic acid component, It may be desirable to remove excess glycol in a subsequent step. However, those skilled in the art will appreciate that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction steps occur.

[00158] For example, in preparing a copolyester by direct esterification from the acid form of a dicarboxylic acid component, the copolyester is prepared by reacting a dicarboxylic acid or a mixture of dicarboxylic acids with a glycol component or a mixture of glycol components. The reaction is carried out at pressures of from about 7 kPa atmospheric pressure (1 psig) to about 1379 kPa atmospheric pressure reference (200 psig), or less than 689 kPa (100 psig) to produce a low molecular weight polymer having an average degree of polymerization of from about 1.4 to about 10. and produce linear or branched copolyester products. The temperature used during the direct esterification reaction is from about 180°C to about 280°C, or from about 220°C to about 270°C. This low molecular weight polymer may be further polymerized by a polycondensation reaction.

[00159] In some embodiments, suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1, 3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[00160] In some embodiments, the following diacid-containing copolyesters are suitable for use in repolymerization processes or polymerization processes to produce new copolyesters with recycled content: terephthalate acids, isophthalic acid, trimellitic anhydride (or trimellitic acid), naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[00161] In some embodiments, suitable for use in polymerization processes or polymerization processes to produce novel copolyesters with recycled content are copolyesters containing the following glycols: ethylene Glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[00162] In one embodiment, recycled waste materials comprising polyester terephthalate and/or copolyesters may be used in the repolymerization process. In one embodiment, any conventionally prepared terephthalate polyester or copolyester may be used in the repolymerization step. In one embodiment, suitable terephthalic and/or copolyesters include polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), acid-modified polycyclohexylene Methylene terephthalate (PCTA), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol terephthalate (PCT), polyethylene naphthalate (PEN), TMCD-modified polyethylene terephthalate (PETM) , TMCD-modified polycyclohexylene dimethylene terephthalate (PCTM), and mixtures thereof. In one embodiment, the polyester terephthalate is polyethylene terephthalate (PET). In one embodiment, the copolyester is PETG. In one embodiment, the copolyester is PCT. In one embodiment, the copolyester is PCTG. In one embodiment, the copolyester is PCTA. In one embodiment, the copolyester is PCTM. In one embodiment, the copolyester is PETM.

[00163] In one embodiment, a mixture of the terephthalate polyester and the copolyester are combined together and repolymerized. In one embodiment, PET and PETG are combined together and repolymerized. In one embodiment, PET and PETM are combined together and repolymerized. In one embodiment, PET and PCT are combined together and repolymerized. In one embodiment, PET and PCTA are combined together and repolymerized. In one embodiment, PET and PCTG are combined together and repolymerized. In one embodiment, PET and PCTM are combined together and repolymerized. In one embodiment, PET and PETG and PETM are combined together and repolymerized. In one embodiment, PET, PETG and PCTM are combined together and repolymerized. In one embodiment, PET, PETG, PCTM, and PETM are combined together and repolymerized.

[00164] In one embodiment, copolyesters suitable for use in the present disclosure include, for example, dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic acid (IPA) 1,4-cyclohexanedicarboxylic acid (CHDA) , ethylene glycol (EG), diethylene glycol (DEG), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD ) are prepared from monomers such as

[00165] One embodiment of the present disclosure repolymerizes waste or post-consumer polyester comprising terephthalic acid-containing polyester (e.g., PET) and/or copolyester (e.g., PETG) with water or alcohol or glycol, and The present invention relates to a process for preparing a copolyester having a high recycled content obtained by using a recycled monomer to prepare a copolyester containing a high mol % of recycled monomer residues.

[00166] One aspect of the present disclosure is a high molecular weight copolyester comprising a glycol component and a diacid component, wherein the glycol component is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2- propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl trans-1,4-cyclohexanedicarboxylate, 1, 6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof wherein the diacid component is dimethyl terephthalate, terephthalic acid, isophthalic acid (IPA), trimellitic anhydride (or trimellitic acid), salts of 5-sulfoisophthalic acid (SIPA), naphthalenedicarboxylic acid, 1, Including 4-cyclohexanedicarboxylic acid, and mixtures thereof. Introduction of depolymerization aids or solvents such as water, alcohols, or excess glycol under conditions where reversible transesterification reactions can occur leads to depolymerization by hydrolysis, alcoholysis, or glycolysis, resulting in polymer chain length (molecular weight) decreases. With a sufficient amount of solvent, the reaction proceeds to the point where the mixture consists primarily of monomers, glycols, and diesters of the acid components. In one aspect, the glycol of the mixture is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1 ,5-pentanediol, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl trans-1,4-cyclohexanedicarboxylate, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2, Including 4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof. In one embodiment, the glycol of the mixture is ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexane Including dimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. In one embodiment, the glycols of the mixture include ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. These recycled monomers can then be used to prepare copolyesters containing a high mole % of recycled monomer residues.

[00167] The present invention utilizes recycled polyethylene terephthalate (PET) and recycled glycol-modified polyethylene terephthalate copolyester (PETG), particularly post-consumer waste, for the production of linear high molecular weight copolyester. Regarding the process to use. There is an increasing desire to use large amounts of recycled materials in plastic articles. This desire for recycled content has created a need to develop new methods and processes for taking existing plastic waste streams and converting them into new plastic products. In particular, there is growing interest in recycling PETG waste. Recent attempts to enact legislation to separate recycled glycol-modified PET (PETG) waste from recycled polyethylene terephthalate (PET) waste with a resin identification code (RIC) of 1 are due to these factors. This is because problems have arisen in the treatment of complex waste. Furthermore, today there is a large amount of unrecycled PETG, which can potentially be recovered and converted into new plastic products. Shrink films made from PETG in particular contain inks and other contaminants that need to be removed in the recycling stream to produce high quality clear recycled PET (rPET). Furthermore, medical packaging is made from a high percentage of PETG, a material that is currently not in the recycling trend. The present invention relates to recycled PETG and PET in the production of copolyesters useful in the production of extruded and injection molded articles such as shrinkable films, fibers, consumer durables, and other moldings and moldings. A process utilizing combined recycled PETG as a reaction intermediate is provided.

[00168] Today, there is a very well defined and large-scale industry where polyethylene terephthalate (PET) articles are recovered and converted to semi-crystalline recycled PET (rPET) and incorporated into new plastic articles. There is a mechanical recycling process. Glycol modification of PET with 1,4-cyclohexanediol, diethylene glycol, butanediol, or other glycols such as neopentyl glycol increases clarity, improves toughness, and reduces the crystallinity of PET. is a very common method for These glycol modified materials are commonly referred to as glycol modified PET or PETG. Although the chemical composition of these materials is very similar to PET, modification with glycols other than ethylene glycol produces materials that are difficult to recycle in PET recycling processes. New methods need to be created to recover and recycle these PETG materials.

[00169] The processes described in this disclosure use recycled PETG as a feedstock to produce a variety of new copolyester resins. In this process, recycled PETG (rPETG) is introduced as a paste along with ethylene glycol and terephthalic acid and fed to a transesterification reactor early in the manufacturing process to produce new copolyester. During this process, the added glycol degrades the rPETG into its original acid and glycol residue starting materials, adding new glycol and acid, then esterifying and polymerizing the mixture to produce new to produce a copolyester. This process has the advantage that recycled PETG can be used as a raw material without the need for further purification of the acids and glycols produced. In addition, this process is valuable as it provides a way to use rPETG that is currently not in the trend of mechanical recycling and therefore can only be buried in landfills.

[00170] In addition, rPETG (or rPCTG, or rPCTM, or rPETM, or rPCTA, or rPCTG, or rPCT) contains expensive monomers with 2 or more valences that are not present in rPET, such as CHDM, TMCD, DEG, and NPG. PETG products produced from this process have the same performance as virgin PETG and can be used in exactly the same applications without sacrificing any performance through the addition of recycled materials. Conventionally, rPETG is blended with virgin material to form a physical mixture. These mixtures often lose performance in terms of mechanical properties or in terms of color and appearance and often cannot be used in the same applications as virgin materials.

[00171] In the synthesis of new PET for manufacturing water and carbonated beverage bottles, it has become commercially desirable to use previously used PET, especially post-consumer PET. Several chemical processing techniques are known to facilitate the recovery and recycling of previously used polyester materials. Such techniques are used to depolymerize recycled polyester material, thereby reducing the polyester material to its monomeric and/or oligomeric components. The monomeric and/or oligomeric components can then be repolymerized to produce a recycled polyester material.

[00172] As one known depolymerization technique, recycled PET is subjected to methanol decomposition. According to the methanolysis procedure, rPET is reacted with methanol to produce dimethyl terephthalate (DMT) and ethylene glycol (EG). DMT and EG can be easily purified and then used to make PET containing recycled polyester materials. However, most conventional commercial PET manufacturing facilities around the world are designed to use either terephthalic acid (TPA), and although there are smaller facilities that use DMT, most The facility was not designed to use both TPA and DMT as monomer feeds. Therefore, additional processing is generally required to convert DMT to TPA, which is required as a raw material for many such facilities, in any case requiring further purification of glycol and DMT/TPA. Become.

[00173] Another known depolymerization technique is hydrolysis, whereby the recycled PET is reacted with water to depolymerize the rPET to TPA and EG. However, it is known to be very difficult and expensive to remove from TPA certain contaminants that are generally present in recycled PET. In addition, facilities designed to use DMT as a feedstock will need to convert TPA to DMT, requiring additional purification of glycol and DMT/TPA.

[00174] Glycolysis may also be used to depolymerize recycled PET. Glycolysis occurs when rPET reacts with EG, thereby producing bis-(2-hydroxyethyl) terephthalate (BHET) and/or its oligomers. Glycolysis has significant advantages over either methanolysis or hydrolysis, primarily because BHET can be converted into either DMT-based or TPA-based PET manufacturing processes without major changes to the manufacturing facility or further purification. This is because it can be used as a raw material. Another important advantage that the glycolytic technique provides is that there is no need to remove the glycol from the depolymerization solvent.

[00175] Conventionally known glycolysis processes include independent and complete glycolysis of post-consumer rPET and subsequent addition of a portion of the glycolysis products to the polycondensation process. This glycololysis process is described in US Pat. No. 5,223,544. This process requires high pressure and a large excess of ethylene glycol. These requirements reduce reactor efficiency by reducing the potential production capacity of the reactor.

[00176] Typically, in these glycololysis processes, high temperatures and large excesses of EG are used to solubilize the polyester molecule and consequently degrade it into its constituent parts such as BHET and its oligomers. turned out to be necessary. This high temperature and excess EG results in large amounts of diethylene glycol as a by-product. Since the diethylene glycol thus produced cannot be easily removed from BHET, when BHET is then used to produce recycled PET, the resulting PET product will have an excessive diethylene glycol content, which has many commercial uses. is an unacceptable polymer for

[00177] Other known processes, including glycolysis, terminate BHET oligomers with a degree of polymerization greater than 10 at the end of the reaction run to solubilize the post-consumer rPET, which is insoluble in most solvents. must be retained in the reactor. These procedures are described in US Pat. No. 4,609,680. Thus, there is clearly still a need in the art for a glycololysis process that can efficiently manipulate previously used post-consumer rPET in the production of new packaging grades of PET.

[00178] The present disclosure provides a solution to the problems discussed above. In particular, the processes of the present disclosure utilize recycled polyesters and/or recycled copolyesters comprising recycled PET, recycled PETG, recycled PETM, and recycled PCTM, or mixtures of these materials. to provide an efficient and economical procedure for producing packaging grade polyester products.

[00179] In one embodiment, the viscosity of the material in and resulting from the kneading zone is significantly reduced by rPETG (and rPCTM or its mixtures with rPET) compared to rPET alone. In one embodiment, TPA dissolves faster in rPET than in EG alone. In one embodiment, TPA can dissolve faster in rPETG, rPETM, or rPCTM.

[00180] In one embodiment, TPA is completely replaced with recycled or copolyester.
[00181] In one embodiment, compositional control of the final polyester product is achieved through the combination of recycled feed and ingredients added to the first reaction zone.

[00182] In one embodiment of the present disclosure, the copolyester is produced in two main stages. In the first stage, the starting materials are reacted to form monomers and/or oligomers. When the starting material entering the first stage contains acid end groups such as TPA or isophthalic acid, the first stage is called esterification. The esterification step may be a single step or divided into multiple steps. In a second stage, the monomers and/or oligomers are further reacted to produce the final copolyester product. The second stage is commonly referred to as the polycondensation stage. The polycondensation step may be a single step or may be divided into a prepolycondensation (or prepolymerization) step and a final (or finishing) polycondensation step.

[00183] FIG. 6 is a process flow diagram for making a polyester or copolyester such as PETG according to various embodiments of the present disclosure. This flow diagram (Figure 6) shows the reaction zones as separate vessels, typically continuous stirred tank reactors (CSTRs), which contain multiple esters with appropriate partitions and controls. It may also be an integral unit with the integrated area. Similarly, although the reaction zones are shown as separate vessels, typically wipe-type or membrane-type CSTRs, these vessels are one with multiple polycondensation zones with appropriate partitions and controls. It may be combined with the above integrated unit. Various other types of esterification and polycondensation reactors and reactor arrangements are known in the art and may be adapted for use in accordance with the present disclosure.

[00184] Referring to FIG. 6, in one embodiment, a paste comprising a 2:1 molar ratio of EG and TPA with recycled copolyester and/or polyester is supplied to a location labeled Paste Vessel. do. Additional EG is fed to the first reaction zone or reactor 1, and other glycols such as CHDM, TMCD, NPG, and DEG are also added to the first reactor at the same location based on the target final composition of the copolyester. The reaction zone may be fed and additional recycled material may also be added as needed. In one embodiment, these ingredients may be added separately and/or directly into the first reaction zone. In some embodiments, recycled copolyester and/or polyester is supplied to at least one location of the paste tank, zone #1, zone #2, or finishing zone. In some embodiments, recycled copolyester and/or polyester is supplied to one or more locations of the paste tank, zone #1, zone #2, or finishing zone.

[00185] The reaction mixture in the first reaction zone is heated via a recycle loop containing a heat exchanger. Esterification occurs in a first reaction zone and a first reaction zone comprising copolyester monomers, oligomers, or both, and unreacted TPA, EG, and other glycols such as CHDM, TMCD, NPG, or DEG. An esterified product is produced. The reaction product of the first reaction zone is then delivered to the second reaction zone. Further esterification occurs in the second reaction zone to form a second esterification product comprising additional copolyester monomers, oligomers, or both.

[00186] In some embodiments, the average chain length of the monomers and/or oligomers at the end of the esterification step may be less than 25, 1-20, or 5-15.
[00187] In one embodiment, the second reaction zone is optional. In some embodiments, the product is delivered from the first reaction zone to the third reaction zone.

[00188] The reaction product of the second reaction zone is then delivered to a third reaction zone. In some embodiments, polycondensation occurs in the third reaction zone, optionally in the presence of a polycondensation catalyst, to produce a prepolymerized product comprising a copolymerized polyester oligomer. In some embodiments, polycondensation occurs in the third reaction zone without the need for a polycondensation catalyst to produce a prepolymerized product comprising a copolymerized polyester oligomer. In some embodiments, the catalyst residues remaining on the recycled copolyesters and polyesters are sufficient to act as polycondensation catalysts. In some embodiments, the third reaction zone converts the monomers from the esterification step to oligomers having average chain lengths in the range of 2-40, 5-35, or 10-30.

[00189] The prepolymerized product is then delivered to one or more reaction zones or finishing zones. Further polycondensation takes place in the finishing section, optionally in the presence of a polycondensation catalyst, to produce a copolyester having the desired average chain length or IV. The copolyester is then recovered from the finishing section and subjected to subsequent processing such as being formed into pellets via an extruder coupled to an underwater pelletizer.

[00190] In one embodiment, the temperature in the kneading vessel is 120-180°C.
[00191] In one embodiment, the temperature in the glycolysis and transesterification zone is 200-300°C.

[00192] In one embodiment, the reacting step is conducted at a melt temperature of at least 253°C, at least 255°C, or at least 257°C. In one embodiment, additionally or alternatively, the reacting step is carried out at a melt temperature of 290°C or lower, 285°C or lower, 280°C or lower, 275°C or lower, 270°C or lower, or 265°C or lower. In various embodiments, the reacting step is conducted at a melt temperature of 250-270°C, or 257-265°C.

[00193] In one embodiment, the reaction step is carried out at a pressure of 25-40 psi, or 30-40 psig.
[00194] In one embodiment, the esterifying step is conducted at a melt temperature of at least 253°C, at least 255°C, or at least 257°C. In one embodiment, additionally or alternatively, the esterifying step is carried out at a melt temperature of 290°C or lower, 285°C or lower, 280°C or lower, 275°C or lower, 270°C or lower, or 265°C or lower. In various embodiments, the esterification step is conducted at a melt temperature of 250-270°C, or 257-265°C.

[00195] In one embodiment, the esterification step (d) is conducted at a pressure of 8-20 psig.
[00196] In one embodiment, the average residence time of the reactants in the reaction step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 less than an hour. In various embodiments, the average residence time of the reactants in the reaction step is from 30 minutes to 40 minutes.

[00197] In one embodiment, the average residence time of the reactants in the esterification step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.5 hours or less. 75 hours or less. In various embodiments, the average residence time of the reactants in the esterification step (d) is 30-40 minutes.

[00198] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 3.0:1.
[00199] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 2.71:1.

[00200] The temperature, pressure, and average residence time for the reaction step in the first reaction zone are as described above.
[00201] In various embodiments, the reaction step in the first reaction zone is conducted at a melt temperature of 250-270°C and a pressure of 25-40 psi.

[00202] In various embodiments, the reaction step in the first reaction zone is conducted at a melt temperature of 257-265°C and a pressure of 30-40 psi.
[00203] The temperature, pressure, and average residence time for the esterification step in the second reaction zone may be as described above.

[00204] In various embodiments, the esterification step in the second reaction zone is conducted at a melt temperature of 250-270°C and a pressure of 8-20 psi.
[00205] In various embodiments, the esterification step in the second reaction zone is conducted at a melt temperature of 257-265°C and a pressure of 8-20 psi.

[00206] Polycondensation catalysts useful in the processes of the present disclosure are not particularly limited. Examples of such catalysts include titanium-based compounds, antimony-based compounds, and germanium-based compounds. Titanium catalysts are very efficient and provide fast polycondensation rates at low catalyst concentrations. The polycondensation catalyst may be added either during the esterification stage or during the polycondensation stage. In one embodiment, the catalysts are added to the first reaction zone along with the feedstock. In one embodiment, the catalyst is added in the range of 1-500 ppm based on the weight of the copolyester. In the case of titanium in one embodiment, the catalyst may be added in the range of 1-50 ppm based on the weight of the copolyester.

[00207] In one embodiment, catalyst selection is influenced by catalysts derived from recycled feedstocks. Certain catalyst benefits are achieved by combining catalyst from the feedstock with catalyst added to the first and second reaction zones. Catalysts likely derived from rPET include Sb, Li/Al. Catalysts derived from rPETG can be Ti, Co, Ge, and Sb. Catalysts obtained from rPETM and rPCTM contain Co.

[00208] In some embodiments, a phosphorus compound is often added with the catalyst to improve thermal stability. Phosphorus compounds useful as heat stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. Esters can be alkyls, branched alkyls, substituted alkyls, difunctional alkyls, alkyl ethers, aryls, and substituted aryls. In some embodiments, suitable heat stabilizers include Merpol A, which is triphenyl phosphate. In one embodiment, phosphorus is added in the range of 10-100 ppm based on the weight of the copolyester.

[00209] In various embodiments, one or more other additives may be added to the starting material, copolyester, and/or copolyester monomer/oligomer at one or more locations within the process. good. In various embodiments, suitable additives include, for example, tri- or tetra-functional additives such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols. pigments; carbon black; glass fibers; fillers; impact modifiers;

[00210] Processes according to the present disclosure are particularly suitable for use on an industrial scale. For example, in one embodiment, the processes may be carried out on commercial production lines capable of operating polymer at rates of 500 to 30,000 pounds per hour.

[00211] In another aspect, the present disclosure relates to copolyesters produced from the processes of the present disclosure.
[00212] Further according to the aforementioned process, the new polyester product may contain ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol diol units, wherein the 1,4-cyclohexanedimethanol units are Containing up to about 25 mol %, the diethylene glycol accounts for up to about 15 mol % of all diol units. In this case, the 1,4-cyclohexanedimethanol units and diethylene glycol units may be added directly to a portion of the ethylene glycol component in the first reaction mixture, post-consumer polyethylene terephthalate or glycol-modified polyethylene terephthalate. may be derived from part of the flake material of

[00213] In various embodiments, the copolyester is
(a) a diacid component comprising 60-100 mole % terephthalic acid residues, isophthalic acid residues, or mixture residues thereof; and (b) 0-96.5 mole % ethylene glycol residues and3. 5 to 100 mol% of a diol component containing 1,4-cyclohexanedimethanol residues,
Here, the diacid component is based on 100 mol % of all diacid residues in the copolyester, and the diol component is based on 100 mol % of all diol residues in the copolyester.

[00214] In various embodiments, the copolyester is
(a) a diacid component comprising 90-100 mol % terephthalic acid residues; and (b) 50-96.5 mol % ethylene glycol residues and 3.5-50 mol % 1,4-cyclohexane diacid. containing a diol component containing methanol residues,
Here, the diacid component is based on 100 mol % of all diacid residues in the copolyester, and the diol component is based on 100 mol % of all diol residues in the copolyester.

[00215] In various embodiments, the copolyester is
(a) a diacid component comprising 90-100 mol% terephthalic acid residues; and (b) 0-50 mol% ethylene glycol residues and 50-100 mol% 1,4-cyclohexanedimethanol residues. containing a diol component containing
Here, the diacid component is based on 100 mol % of all diacid residues in the copolyester, and the diol component is based on 100 mol % of all diol residues in the copolyester.

[00216] In various embodiments, the copolyester is
(a) a diacid component comprising 60-100 mole % terephthalic acid residues; and (b) 65-85 mole % residues of ethylene glycol and 25-35 mole % residues of 1,4-cyclohexanedimethanol. containing a diol component containing
Here, the diacid component is based on 100 mol % of all diacid residues in the copolyester, and the diol component is based on 100 mol % of all diol residues in the copolyester.

[00217] In various embodiments, the copolyester has an intrinsic viscosity of 0.4 to 1.5 dL/g, or 0.5 to 1.2 dL/g, or 0.6 to 0.9 dL/g.
[00218] In various other embodiments, the copolyester is
(a) a diacid component comprising 100 mole % terephthalic acid residues, isophthalic acid residues, or mixture residues thereof; and (b) 0-96.5 mole % ethylene glycol residues, 3.5- a diol component comprising 100 mol% 1,4-cyclohexanedimethanol residues and 0-0.4 mol% trimellitic anhydride residues;
Here, the copolyester has an intrinsic viscosity (IV) of 0.4 to 1.5 dL/g,
All weight percentages are based on the total weight of the copolyester, and the diacid component is based on 100 mole% of total diacid residues in the copolyester, and the diol component is based on 100 mole% of the copolyester. Based on all diol residues.

[00219] In one embodiment, the present disclosure includes articles of manufacture or molded that include the shrink film of any of the shrink film embodiments of the present disclosure. In another embodiment, the present disclosure includes an article of manufacture or molded comprising an oriented film of any of the oriented film embodiments of the present disclosure.

[00220] In certain embodiments, the present disclosure provides shrink films suitable for, but not limited to, containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and/or industrial or other applications. include. In one embodiment, the present disclosure provides orientations that are compatible with, but not limited to, containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, hot-fill containers, and/or industrial products or other applications. Including film.

[00221] In certain embodiments of the present disclosure, the shrink films of the present disclosure may be formed into labels or sleeves. The label or sleeve may then be applied to the wall of the container, the article of manufacture such as the battery, or over the sheet or film.

[00222] Oriented or shrinkable films of the present disclosure can be applied to shaped articles such as sheets, films, tubes, bottles, etc., and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyesters, polylactic acid (PLA) are frequently used in the production of shrink labels for plastic beverage or food containers. For example, the shrink films of the present disclosure can be used in many packaging applications in which the shrink films applied to molded articles exhibit excellent printability, high opacity, excellent shrink force, excellent texture, and It exhibits properties such as high rigidity.

[00223] The combination of improved shrink properties and improved toughness results in compliant shrinkage for, but not limited to, containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and/or industrial or other applications. It should offer new commercial options, including film.

[00224] Additionally, the materials of the present disclosure may be extruded into sheets, which may further be thermoformed into three-dimensional articles. Materials of the present disclosure may be converted into molded articles, films, shrinkable films, oriented films, blow molded articles, and blown film articles.

[00225] The present disclosure includes, and expressly contemplates and discloses, any and all combinations of the embodiments, features, properties, parameters, and/or ranges described herein. That is, the subject matter of this disclosure can be defined by any combination of the embodiments, features, properties, parameters, and/or ranges described herein.

[00226] Any process/method, apparatus, compound, composition, embodiment, or component of the disclosure "comprising," "consisting essentially of, or "consisting of, or variations of those terms. may be modified by a transitional clause that is

[00227] As used herein, the indefinite articles "a" and "an" mean one or more, unless the context clearly dictates otherwise. Similarly, the singular form of a noun includes its plural form and vice versa unless the context clearly dictates otherwise.

[00228] Although attempts have been made to be precise, the numerical values and ranges set forth herein should be considered approximations unless the context dictates otherwise. These numbers and ranges may vary from those stated depending on the desired properties sought to be obtained by this disclosure and variations due to standard deviations found in measurement techniques. Moreover, ranges recited herein are intended and specifically contemplated to include all subranges and values within the recited range. For example, the range 50-100 is intended to include all numbers within the range, including subranges such as 60-90, 70-80, and so on.

[00229] A range may be defined by any two numerical values for the same property or parameter reported in the examples. These numbers may be rounded to the nearest thousandths, hundredths, tenths, integers, tens, hundreds, or thousands to define ranges.

[00230] The contents of all documents cited herein, including patent and non-patent literature, are hereby incorporated by reference in their entirety. To the extent any incorporated subject matter conflicts with any disclosure herein, the disclosure herein shall control over the incorporated content.

[00231] The disclosure may be further illustrated by the following examples, which, of course, are included for illustrative purposes only and are intended to limit the scope of the disclosure. No. Unless indicated otherwise, parts are parts by weight, temperature is in degrees Celsius or is at room temperature, and pressure is at or near atmospheric.

[00232] The present disclosure is further illustrated by the following examples of its implementation, which, of course, are included for illustrative purposes only and limit the scope of the present disclosure unless otherwise indicated. is not intended to be

Comparative example 1
[00233] The shrink film properties of a standard polyester shrink film resin (Sample SPR) are shown in Table 1 (this standard resin is commercially available from Eastman Chemical Company). A shrink film made using this standard shrink film resin is referred to as Comparative Example #1.

[00234] Shrinkage properties are shown in Figure 2, where shrinkage is measured in the primary shrink direction (TD) and in the direction perpendicular to the primary shrink direction (MD) over a temperature range of 60-95°C. The melting point of strain-induced crystals is measured using differential scanning calorimetry (DSC) on stretched films (Fig. 1). A pellet sample can also be crystallized in an oven at 170° C. for 2 hours to assess the crystallinity of the sample. The melting point of strain-induced crystals is measured by first heating at a heating rate of 20° C./min, whereas the resins described in this disclosure are typically subjected to a DSC procedure with a heating rate of 20° C./min. It has no measurable crystalline melting point on the second heating.

[00235] The Association of Plastics Recyclers (APR) has established a test to determine whether a material is compatible with the current recycling process (PET-CG-03). Using this test method, labels (minimum weight: 3% by weight) and bottles were crushed to a flake size of 1/4 to 1/2 inch. This bottle flake was then mixed 50:50 with an unlabeled reference bottle flake. This sample was then wet classified under conditions that allowed no more than 1.2% PET to carry over with the label. The slices were washed with 0.3% Triton X-100 and 1.0% caustic at 88°C for 15 minutes. The flakes were then washed with water after all suspended matter was removed and then filtered to remove excess water. The flakes were again wet classified as before. Two pounds of washed flakes were then placed in a Teflon lined baking dish for each washed sample and additional flakes were added to a 1.5 inch layer thickness. The dish containing the flakes was placed in a circulating oven at 208° C. for 1.5 hours. The flakes were cooled and then passed through a screen with 0.0625 inch openings. If the material passes through the sieve, it is not agglomerated or too coarse to pass through the sieve. This test was followed by extrusion/pelletization and molding steps to confirm flake quality.

[00236] The film samples described in Table 1 yield greater than 1% by weight agglomerated PET flakes using this APR test and are therefore approved for use in PET recycling. Labels made with this type of resin therefore need to be removed prior to the PET recycling process to eliminate agglomeration of the PET flakes after processing. However, since the crystallizable film of the present disclosure is more compatible with the recycling process and can be recycled along with the PET flakes, the crystallizable film composition will benefit in the recycling process. will provide.

[00237] The crystallizable compositions described in this disclosure were designed to be compatible with recycling processes. In order to be compatible with the recycling process, the crystallizable film is designed not to become "sticky" during the drying process at 208°C, as described in the APR test. However, the film must also meet the performance criteria typically required for shrink films (high maximum shrinkage, low to negative MD shrinkage, etc.). In order to meet these requirements, i.e. both recyclability and good shrinkage properties, the polyester composition must be amorphous, i. The composition should be free of crystallinity as measured using a heating of . However, after stretching, the films made with the optimized polyester resin composition show a wide range of temperatures above 200°C measured during the first heat using a DSC operating at a heating rate of 20°C per minute. must contain the melting peak of the strain-induced crystal of This degree of strain-induced crystallinity can prevent stickiness during the drying process associated with recycled PET flakes. Thus, the optimized polyester resin composition of the present disclosure can be described as amorphous but crystallizable.

[00238] The following examples further demonstrate how the polyesters of the present disclosure can be made and evaluated, and are intended to be purely illustrative and not intended to limit the scope thereof. No. Unless indicated otherwise, parts are parts by weight, temperature is in degrees Celsius or is at room temperature, and pressure is at or near atmospheric.

[00239] The present disclosure can be further illustrated by the following examples of preferred embodiments thereof, but it should be understood that these examples are included for illustrative purposes only and unless otherwise indicated. is not intended to limit the scope of

Example 1
[00240] To better understand these performance goals, a series of copolyesters with varying CHDM and DEG contents were prepared using procedures well known to those skilled in the art of making polyesters. After synthesis, these resins were ground into powders and compressed into 10 mil film samples using a hot press. The compressed film was then stretched using a Bruckner film stretcher so that the properties of the shrink film could be measured. The ground sample was crystallized at 170° C. for 2 hours in a forced air circulation oven so that the crystalline melting point could be determined. This crystallized sample was used as a surrogate for the strain-induced crystal melting peak present after stretching. Table 2 summarizes the experimental details. Comparative Example 1 (film #L-1/resin sample SPR) was prepared and evaluated as a control.

[00241] The data in Table 2 show that resin samples with an amorphous monomer content of less than 24 (DEG + CHDM in this case) have a crystalline melting peak above 200°C after heat treatment. The composition of Film #L-5 was then scaled up in a larger reactor to make a shrink film on a commercial tenter. The shrinkage properties of this film are shown in FIG. 3 together with the sample of Comparative Example 1 (Resin SPR). The composition of Film A was the same as Film #L-5.

[00242] Table 3 summarizes the comparison between Sample SPR and Film Sample A. This data shows that the Film A composition does not shrink in a manner similar to Comparative Example #1. The maximum shrinkage (the shrinkage in the main shrinkage direction or TD at 95°C) is 17% lower than Comparative Example #1. Furthermore, the shrinkage ratio in the direction perpendicular to the main shrinkage direction (MD shrinkage ratio) is actually positive (7%) in Sample A compared to Comparative Example #1. Positive MD shrinkage is not preferred.

Example 2
[00243] Neopentyl glycol (NPG) is another glycol monomer that can produce amorphous copolyester compositions. It was believed that MD shrinkage could be reduced by adding NPG instead of CHDM. To investigate this effect in more detail, another resin sample of similar composition was made containing NPG instead of CHDM. This new resin sample was mixed with the resin used to make L-5 to study the effects of monomer substitution. These resins were extruded into 10 mil films and then stretched on a Bruckner film stretcher. Testing of these films gave the following results: MD shrinkage at 75°C is 0% when the CHDM content is less than 8 mol%; , MD shrinkage becomes negative, indicating dilation instead of shrinkage. Furthermore, the effect of amorphous monomer content was confirmed. All samples shown in Table 4 have an amorphous monomer content greater than 23. Subsequently, the strain-induced crystal melting points of these compositions were below 200°C. The melting point of this strain-induced crystal below 200° C. is too low to pass the APR test. Typically, the strain-induced crystal must have a melting point above 200° C. to pass the APR test. From this study, it was determined that further reductions in amorphous monomer were needed to ensure a strain-induced crystal melting point above 200°C. In some cases, the CHDM content should be less than 10 mol % to ensure the production of films with minimal shrinkage in the direction perpendicular to the main shrinkage direction (MD direction).

Example 3
[00244] A series of resins were then prepared and extruded into 10 mil films using a 2.5 inch Davis and Standard extruder, stretched and then evaluated for their shrink film performance and shrink characteristics. and crystallinity were compared. Details of these resin compositions and the performance of shrink films made from these resin compositions are shown in Table 5. From this analysis, an optimal resin composition was designed that yielded low MD shrinkage at 75°C and a strain-induced crystal melting point above 200°C. This optimized resin composition contains 10 mol % NPG, 5 mol % CHDM and 5 mol % DEG. Again, resins containing less than 24 mol % amorphous monomer content were determined to have a strain-induced crystalline melting point of 200° C. or higher. MD shrinkage is minimized when the content of CHDM monomer is less than 10 mol %.

Example 4
[00245] Several of these resins were then tested in a flocculation test that mimics the APR protocol to assess the effect of melting point (Tm) on flocculation. The parameters of the aggregation test are as follows.
- Approximately 135 g of PET flake per sample; and approximately 3.4 g of shrink film in its shrunk state (2.5% film with flake).
• PET flakes and films were placed in aluminum pans to a depth of 1.5 inches.
• The dish with the flakes was placed in a forced air circulation oven at an oven temperature of 208°C for 1.5 hours.

[00246] The results of these tests are set forth in Table 7.

Comparative example 2
[00247] Films made from these compositions with an amorphous monomer content of less than 20 (and thus a DEG content of less than 12) were also very tough. The toughness of these films is measured using ASTM method D882. A film having an elongation to break of greater than 300% at a tensile speed of 300 mm/min and even at a tensile speed of 500 mm/min is considered tough.

[00248] Other film structures can be used to make these crystallizable polyester shrink film resins. For example, a multilayer film may be formed such that the core of the film is made from one amorphous shrink film resin (e.g., Comparative Example #1) and the skin is made from the crystallizable shrink film resin of the present disclosure. good. In this construction, the properties of the shrink film are similar to those of the core layer, but the skin exhibits a degree of crystallinity that may reduce the amount of agglomeration during recycling. Additionally, mixtures of various commercially available resin compositions may be made to replicate the resin composition of the reactor grade resin. In either case, the performance of the resulting shrink film should be evaluated for effectiveness in shrink film applications. Table 12 shows the construction of these shrink films. These films were produced on a commercial tenter and evaluated for their performance in shrink film applications.

[00249] Standard sample E21, sample E12, sample SP, and sample SPR were evaluated. All standards evaluated are commercially available from Eastman Chemical Company. Sample E226, Sample E213, and Sample E2616 were made in the laboratory using procedures well known to those skilled in the art of making copolyesters.

[00250] As can be seen in these mixture examples, many of the properties of the resulting shrink films meet the desired properties of the compositions of the present disclosure. However, two of the film examples have high MD shrinkage at 75°C. However, in these examples, the strain-induced crystal has a higher melting point (235-240° C.). This higher strain-induced crystal melting point can be advantageous in applications requiring higher melting points, but these higher melting points result in higher MD shrinkage, so a balance of properties is needed.
Exam details
[00251] The resin samples were dried in a dehumidified dryer at 60°C, then mixed and extruded into films using two different processes. In the lab scale extruder process, a 2.5 inch Davis and Standard extruder was used to extrude a 10 mil (250 μm) thick film. After extrusion the film was cut and stretched in a Bruckner Karo 4 tenter at 10-15°C above Tg to a final thickness of 50 µm at a draw ratio of about 5:1. In a commercial process, the film was produced in a commercial tentering process in which the extruded film was stretched immediately after extrusion. These films were stretched to a thickness of 50 μm at a stretch ratio of approximately 5:1 under conditions nearly identical to the films produced in the laboratory scale process.

[00252] In the experimental scale compressed film process, the resin is dried overnight (about 12 hours) under vacuum in an oven set at a temperature just below the Tg of the material. After drying, 8.00 g of resin was weighed and placed between two metal plates according to a plate-Kapton film-resin-Kapton film-plate configuration surrounded by a 10 mil square gap plate. Prior to inserting this construction into the press, the platen of the press is heated to a temperature approximately 100° C. above the Tm of the resin. The composition is then inserted between the platens of the press and enough force is applied to the plates to completely melt the resin. After the resin has melted for 3 minutes, the pressure is increased to 12,000 psi over 1.5 minutes. A "bubble bump" procedure is then performed. release pressure from 12,000 psi to 0 psi and increase to 13,000 psi; immediately release pressure again to 0 psi and increase to 14,000 psi; repeat increments of 1000 psi until 16,000 psi is achieved and 16, A 1.5 minute hold of 000 psi pressure is performed. The resin/plate assembly is then removed from the press and pulled from the shimming plate using a razor blade. The result is a 6 x 6 square 10 mil film suitable for stretching on a Bruckner tenter.

[00253] The glycol content of the extruded film compositions was measured by NMR. All NMR spectra were analyzed with chloroform-trifluoroacetic acid (70-30 v/v) for polymers, or 60/40 (w/w) phenol for oligomer samples, with deuterated chloroform added for locking. / Tetrachloroethane were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer. The acid component of the mixed polymer used in the examples herein was 100 mole % terephthalic acid. The total mol % of the glycol component was equal to 100 mol % and the total mol % of the acid component was equal to 100 mol %.

[00254] The intrinsic viscosity of the polyester herein was measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 mL at 25°C. The viscosity is given in dL/g.

[00255] Shrinkage is measured herein by placing a 100 mm x 100 mm square film sample in water at 65°C to 95°C for 10 seconds without restricting shrinkage in any direction. At that time, the shrinkage rate is calculated by the following formula.

Shrinkage rate (%)=[(100 mm−length after shrinkage)/100 mm]×100%.
[00256] Shrinkage was measured in the direction perpendicular to the primary shrink direction (machine direction: MD) and in the primary shrink direction (transverse direction: TD).

[00257] Shrink force was measured in MPa in the examples herein using a LabThink FST-02 heat shrink tester.
[00258] Tensile film properties were measured for the examples herein using ASTM Method D882. Films were evaluated using multiple film stretching speeds (300 mm/min and 500 mm/min).

[00259] The glass transition temperature of polyesters and the melting point of strain-induced crystals (Tg and Tm, respectively) are measured using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C/min. The Tm was measured on the first heat of the stretched sample and the Tg was measured during the second heating step. Additionally, samples can be crystallized in a forced air circulation oven at 170° C. for 2 hours and then analyzed by DSC. For all samples, the crystalline melting point is typically absent during the second heating of the DSC scan at a heating rate of 20°C/min.

[00260] Although the present disclosure has been described in detail with particular reference to preferred embodiments thereof, it will be appreciated that numerous variations and modifications can be effected within the spirit and scope of the disclosure.
Experimental Scale Process Results
[00261] General procedure: A mixture of 53.16 g PTA, 62.21 g EG, 2.97 g DEG, 11.52 g CHDM, and 18.86 g rPET was added to a nitrogen inlet, metal stirrer, and a 500 mL flask equipped with a short distillation column. Additionally, 0.14 mL of Ti catalyst solution (targeting 16 ppm Ti) and 1 mL of Mn solution (targeting 45 ppm Mn) were added to the flask. The flask was placed in a Wood's metal bath preheated to 200°C. The stirring speed at the beginning of the experiment was set at 200 rpm. The contents of the flask were heated at 200° C. for 60 minutes, followed by a gradual temperature increase to 250° C. over 300 minutes. The stirrer was then reduced to 100 rpm and the reaction mixture was heated to 270° C. for 20 minutes while gradually increasing the vacuum to 0.4 torr. The temperature was then raised to 278° C. over 20 minutes, the agitation was reduced to 60 rpm and the mixture was held at this condition for 120 minutes. After this hold, the mixture was returned to atmospheric pressure and cooled. The polymer was then removed from the flask and analyzed. Example 1 was prepared by substituting 100% of TPA with rPET. Example 2 was prepared by substituting 20% of TPA with rPET.

[00262] In one aspect of the present disclosure, under reasonably constant rPET feed conditions, the amount of Sb and other residual catalysts and additives can be predicted as shown in FIG. In some embodiments, FIG. 7 shows the amount of antimony that needs to be added into the system to balance based on the amount of rPET fed into the process. For example, 60% rPET can be fed into the process if 100 ppm Sb is in the final product, or 60 ppm Sb is added to the system if 20% rPET is fed.

[00263] The resins produced in both examples were similar with respect to all key performance criteria. Both materials had similar color, IV, and composition regardless of the amount of rPET added.
Test factory process results
[00264] In a reactor containing 45.7 wt% ethylene glycol, 0.7 wt% diethylene glycol, 9.8 wt% 1,4-cyclohexanedimethanol, and 36.4 wt% terephthalic acid, 7 Resin samples (A1 and A2) were prepared with the addition of .3% by weight of recycled PET. Ti catalyst was added at 30 ppm. The glycol to acid ratio was 3.3 and excesses of ethylene glycol and 1,4-cyclohexanedimethanol were used. The reaction mixture was held at 250-255° C. and 25-30 psig for 3-3.5 hours. Phosphorus was added at 21 ppm, then the reaction mixture was heated to 270° C. and stirred under vacuum until the target melt viscosity was reached.

[00265] A control resin sample (B) was made using the same process, except that 50 ppm Ti catalyst was used without the addition of rPET or DEG to the reaction mixture. 44.1 wt% ethylene glycol, 10.5 wt% 1,4-cyclohexanedimethanol, and 45.5 wt% terephthalic acid were charged to the reactor. The glycol to acid ratio was 2.9 and excesses of ethylene glycol and 1,4-cyclohexanedimethanol were used. The CHDM excess was the same as the above sample, but the EG excess was reduced.

[00266] The properties of these resins are set forth in the table below.

[00267] Resin Examples A1 and A2 were mixed to form Resin A. Resins A and B were dried in a 60° C. oven for 4-6 hours. Films having a thickness of 10 mils (250 μm) were then extruded using a 2.5 inch Davis and Standard extruder. After extrusion, the film was cut and stretched on a Bruckner Karo 4 tenter to a final thickness of 50 μm. The film was stretched at a ratio of 5:1, a stretch rate of 100%/sec and a stretch temperature of 5-15° C. above the Tg of the extruded film. Characterization of the shrinkable films produced by this process is set forth in the table below.

[00268] Resins A and B were very similar in composition, IV, and color. Shrinkable films made with these resins also showed very similar performance. These results demonstrate that the incorporation of rPET into the resin manufacturing process does not affect the final performance of the resin or articles made from the resin.
commercial scale process
[00269] Resin samples were also produced on commercial manufacturing equipment to demonstrate the utility of the present invention.

[00270] In the commercial scale process, 5% recycled PET was added along with terephthalic acid and ethylene glycol. The slurry reservoir was agitated for 30 minutes or longer to allow thorough mixing. This slurry was then added to reaction zone 1 along with catalyst, additional ethylene glycol, diethylene glycol, and cyclohexanediol. The mixture was reacted at a pressure of 35+psig and above 235° C. for at least 1 hour while depolymerizing the PET and reacting the monomers. Monomers and oligomers from Reaction Zone 1 were then delivered to Reaction Zone 2 where they were further reacted while removing additional glycol while maintaining the reaction temperature. This material was delivered into reaction zone 3 and subjected to finishing treatment under higher temperature and higher vacuum conditions. The properties of the final product, Example C, are shown in the table below in comparison to Example D, another copolyester resin of the same composition made in a commercial process without the addition of rPET.

[00271] Resins C and D were dried in a 60°C oven for 4-6 hours. Films having a thickness of 10 mils (250 μm) were then extruded using a 2.5 inch Davis and Standard extruder. After extrusion, the film was cut and stretched on a Bruckner Karo 4 tenter to a final thickness of 50 μm. The film was stretched at a ratio of 5:1 at a stretching rate of 100%/sec and a stretching temperature of 5-15°C above the Tg of the extruded film. Characterization of the shrinkable films produced by this process is set forth in the table below.

[00272] Resins C and D were very similar in composition, IV, and color. Shrink films made with these resins also retained very similar performance. These results demonstrate that the incorporation of rPET within the resin manufacturing process does not affect the final performance of the resin or articles made from the resin.

[00273] Although the disclosure has been described in detail with particular reference to particular embodiments thereof, it will be appreciated that variations and modifications may be effected within the spirit and scope of the disclosure.

Claims (20)

A process for producing a polyester composition from recycled polyester,
(a) recycled resources comprising terephthalic acid (TPA) and ethylene glycol (EG) and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG introducing the modified polyester into a paste vessel and stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to a first reaction zone;
(c) introducing into said first reaction zone at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); adding additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as appropriate; and additional terephthalic acid (TPA) and ethylene glycol (EG) such that the total glycol:TPA molar ratio is from 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer. adding;
(d) in said first reaction zone, said TPA and EG and recycled polyester are reacted with said at least one additional glycol at a melt temperature of at least 200° C. to produce oligomers and unreacted TPA; producing an esterification product comprising EG and said additional glycol;
(e) optionally delivering said esterification product to a second reaction zone;
(f) in said second reaction zone additional glycols optionally comprising at least one of CHDM, NPG or DEG and/or recycled PET, recycled PETG, recycled PCT , recycled PCTA, or recycled PCTG, and optionally in the presence of an esterification catalyst and/or stabilizer at a temperature of at least 200°C. further reacting the esterification product at a melt temperature to produce a resulting esterification product comprising a polyester oligomer;
(g) delivering said resulting esterified product from one or more reaction zones to a third reaction zone; and (h) optionally recycling within said third reaction zone. adding additional recycled polyester comprising one or more of PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, the resulting esterified product comprising: A process comprising polycondensing, optionally in the presence of a polycondensation catalyst and/or stabilizer, to produce a polymerization product comprising a polyester. A process for producing a polyester composition from recycled polyester,
(a) introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste bath, stirring and heating at a temperature of up to 150° C. to form a slurry;
(b) delivering the paste bath slurry to a first reaction zone;
(c) introducing into said first reaction zone at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally total glycol: moles of TPA adding additional terephthalic acid (TPA) and ethylene glycol (EG) in a ratio of 1:1 to 4:1, optionally in the presence of an esterification catalyst and/or stabilizer;
(d) in said first reaction zone, said TPA and EG and recycled polyester are reacted with said at least one additional glycol at a melting temperature of at least 175° C. to form oligomers and unreacted TPA; producing an esterification product comprising EG and said additional glycol;
(e) optionally delivering said esterification product to a second reaction zone;
(f) optionally in said second reaction zone, additional glycol and/or recycled PET, recycled PETG, optionally comprising one or more of CHDM, NPG, or DEG; adding additional recycled polyester comprising one or more of recycled PCT, recycled PCTA, or recycled PCTG, optionally in the presence of an esterification catalyst and/or stabilizer, further reacting said esterification product at a melting temperature of at least 200° C. to produce a resulting esterification product comprising polyester oligomers;
(g) delivering said resulting esterified product to a third reaction zone; and (h) optionally within said third reaction zone recycled PET, recycled PETG, recycled adding additional recycled polyester comprising one or more of recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM, said resulting esterification product optionally in the presence of a polycondensation catalyst and/or stabilizer to produce a polymerization product comprising a polyester. 3. A polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein the at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
about 75 mol % or more of ethylene glycol residues; and (i) about 0 to less than about 24 mol % of neopentyl glycol residues;
(ii) from about 0 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 10 mole percent of total diethylene glycol residues in the final polyester composition. wherein the total mole % of said dicarboxylic acid component is 100 mole % and the total mole % of said diol component is 100 mole %; or (b) Diol component containing:
about 75 mol % or more of ethylene glycol residues; and (i) about 0.1 to less than about 24 mol % of neopentyl glycol residues;
(ii) from about 0.1 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 10 mole percent of the total diethylene glycol residues in the final polyester composition. up to about 25 mol % of other glycols, including one or more
A polyester composition wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms and (b ) diol component containing:
about 75 mol % or more of ethylene glycol residues; and (i) about 0 to less than about 24 mol % of neopentyl glycol residues;
(ii) from about 0 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 10 mole percent of total diethylene glycol residues in the final polyester composition. up to about 25 mol% of other glycols, including
or (b) a diol component comprising:
about 75 mol % or more of ethylene glycol residues; and (i) about 0.1 to less than about 24 mol % of neopentyl glycol residues;
(ii) from about 0.1 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 10 mole percent of the total diethylene glycol residues in the final polyester composition. up to about 25 mol % of other glycols, including one or more
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
about 75 mol% or more of ethylene glycol residues, and (i) about 15 mol% or less of neopentyl glycol residues,
(ii) about 5 mole percent or less of 1,4-cyclohexanedimethanol residues; and (iii) about 5 mole percent or less of total diethylene glycol residues in the final polyester composition. % other glycols,
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
about 80 mol% or more of ethylene glycol residues; and (i) about 5 to less than about 17 mol% of neopentyl glycol residues;
(ii) from about 2 to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 5 mole percent of total diethylene glycol residues in the final polyester composition. up to about 20 mol % of other glycols, including
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
about 76 mol% or more of ethylene glycol residues, and (i) neopentyl glycol residues,
(ii) cyclohexanedimethanol residues, and (iii) an amorphous content of up to about 24 mole percent comprising one or more of diethylene glycol residues in the final polyester composition;
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
greater than or equal to about 75 mole percent ethylene glycol residues; and (i) less than about 10 to about 15 mole percent neopentyl glycol residues;
(ii) from about 1 to less than about 5 mole percent 1,4-cyclohexanedimethanol residues; and (iii) from about 1 to less than about 5 mole percent of total diethylene glycol residues in the final polyester composition. up to about 25 mol% of other glycols, including
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. A crystallizable or thermoformable film or sheet comprising a polyester composition comprising at least one polyester made from recycled polyester by the process of claim 1 or 2, wherein said at least one polyester is
(a) a dicarboxylic acid component comprising:
(i) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; b) a diol component containing:
(i) from about 0 to about 30 mol % of neopentyl glycol residues;
(ii) from about 0 to less than about 30 mole percent 1,4-cyclohexanedimethanol residues, and (iii) diethylene glycol residues, whether formed in situ or not,
The remainder of the glycol component is
(iv) ethylene glycol residues, and (v) optionally 0 to 10 mol % or 0 to 5 mol % of at least one modified glycol,
A crystallizable or thermoformed film or sheet wherein the total mole percent of said dicarboxylic acid component is 100 mole percent and the total mole percent of said diol component is 100 mole percent. The intrinsic viscosity of said polyester is between 0.50 and 0.80 dL/g when measured in 60/40 (wt/wt) phenol/tetrachloroethane at 25°C and a concentration of 0.25 g/50 mL. A crystallizable or thermoformable film or sheet according to any one of Items 1-9. 11. The polyester of any one of claims 1-10, wherein the polyester has a Tg of 65°C to 80°C when measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C/min. A crystallizable or thermoformable film or sheet as described. The total diol content of the one or more diol monomer components capable of producing an amorphous component in said final polyester is 5 to 25 mol % with respect to the total diol content being 100 mol %; the total diol content of the one or more diol monomer components capable of producing an amorphous component in said final polyester is 10 to 20 mol % with respect to the total diol content being 100 mol %; The total diol content of the one or more diol monomer components that can produce the component is 15-20 mol% with respect to the total diol content being 100 mol%; alternatively the amorphous component can be produced in said final polyester Crystallizable according to any one of claims 1 to 11, wherein the total diol content of the one or more diol monomer components is 15-25 mol% with respect to the total diol content being 100 mol%. Films or thermoformed films or sheets. The total diol content of said 1,4-cyclohexanedimethanol residues and said neopentyl glycol residues in said final polyester is 5-25 mol %, 5-15 mol with respect to the total diol content being 100 mol % %, from 10 to 15 mol %, from 10 to 20 mol %, or from 5 to 20 mol %, or from greater than 5 mol % to less than 20 mol %; mol %, said diethylene glycol residues are present in an amount of 2-10 mol %, said neopentyl glycol residues are present in an amount of 5-20 mol %, and said ethylene glycol residues are present in an amount of 75 or the 1,4-cyclohexanedimethanol residue is present in an amount of 2-5 mol%, the diethylene glycol residue is present in an amount of 5 mol% or less, and the neopentyl Crystallizable film according to any one of the preceding claims, wherein glycol residues are present in an amount of 10-15 mol% and said ethylene glycol residues are present in an amount of more than 75 mol%. Or a thermoformed film or sheet. The total crystallizable polyester component diol content of said 1,4-cyclohexanedimethanol residues and said neopentyl glycol residues in said final polyester is 4 to 15 with respect to the total diol content being 100 mole %. 12. The crystallizable or thermoformed film of any one of claims 1 to 11, which is mol%, 1 to 25 mol%, 2 to 20 mol%, or more than 2 mol% to less than 20 mol%. or sheet. The film or sheet is stretched in at least one direction and the stretched film or sheet has a strain-induced crystalline melting point of 170° C. or more, or the film or sheet is stretched in at least one direction and stretched film or sheet A crystallizable or thermoformed film or sheet according to any one of the preceding claims, wherein the sheet has a strain-induced crystalline melting point of 200°C or higher. A method of introducing or forming recycled content in a polyester produced by the process of claim 1, comprising:
(a) obtaining a recycled monomer quota or limit for at least one recycled monomer comprising TPA, EG, DMT, CHDM, NPG, or DEG;
(b) converting the recycled monomers in the synthesis process to produce a polyester;
(c) designating at least a portion of said polyester as corresponding to at least a portion of said recycling monomer quota or limit; and (d) optionally said recycling corresponding to that designation. marketing or selling said polyester as containing or obtained using a content of monomers. A process according to claim 1 or 2, wherein the amount of recycled polyester added to the process is 5-100% based on the amount of TPA required. 3. The process of claim 1 or 2, wherein the esterification catalyst comprises one or more of Mn, Ti, Zn, Co, Ge, or Al. 3. The polycondensation catalyst of claim 1 or 2, wherein the polycondensation catalyst comprises one or more of Sn, Sb, Ti, Li/Al, Al, Ge, Pb, Zn, Co, Bi, Cd, Ca, or Ni. process. Said process further comprises adding a catalyst or additive by addition of the recycled polyester, said catalyst or additive comprising Sb, Ti, Co, Mn, Li, Al, P.I. 3. The process of claim 1 or 2, which is a component of recycled polyester such as.

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